WO2014117663A1 - 石英砂/石墨复合熔盐传热蓄热介质及其制备方法 - Google Patents

石英砂/石墨复合熔盐传热蓄热介质及其制备方法 Download PDF

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WO2014117663A1
WO2014117663A1 PCT/CN2014/070970 CN2014070970W WO2014117663A1 WO 2014117663 A1 WO2014117663 A1 WO 2014117663A1 CN 2014070970 W CN2014070970 W CN 2014070970W WO 2014117663 A1 WO2014117663 A1 WO 2014117663A1
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Prior art keywords
parts
heat
molten salt
heat transfer
nitrate
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PCT/CN2014/070970
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English (en)
French (fr)
Inventor
曾智勇
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Shenzhen Enesoon Science and Technology Co Ltd
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Shenzhen Enesoon Science and Technology Co Ltd
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Priority claimed from CN201310040070.5A external-priority patent/CN103911119B/zh
Priority claimed from CN201310040909.5A external-priority patent/CN103923618B/zh
Priority claimed from CN201310731924.4A external-priority patent/CN103911120B/zh
Priority claimed from CN201310732738.2A external-priority patent/CN103923612B/zh
Application filed by Shenzhen Enesoon Science and Technology Co Ltd filed Critical Shenzhen Enesoon Science and Technology Co Ltd
Priority to US14/765,295 priority Critical patent/US10865335B2/en
Priority to EP14745627.1A priority patent/EP2952551B1/en
Priority to ES14745627T priority patent/ES2848832T3/es
Publication of WO2014117663A1 publication Critical patent/WO2014117663A1/zh
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/08—Materials not undergoing a change of physical state when used
    • C09K5/10—Liquid materials
    • C09K5/12—Molten materials, i.e. materials solid at room temperature, e.g. metals or salts
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/02—Materials undergoing a change of physical state when used
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/02—Materials undergoing a change of physical state when used
    • C09K5/06—Materials undergoing a change of physical state when used the change of state being from liquid to solid or vice versa
    • C09K5/063—Materials absorbing or liberating heat during crystallisation; Heat storage materials

Definitions

  • the invention relates to a heat storage heat transfer composite medium for solar thermal power generation, in particular to a molten salt heat transfer heat storage medium compounded with quartz sand or graphite and a preparation method thereof.
  • the heat storage heat transfer medium currently used mainly includes air, water, heat transfer oil, molten salt, sodium and aluminum metal.
  • Molten salt has a wide range of operating temperature range, low vapor pressure, low viscosity, good stability, low cost and many other features that have become potential heat transfer and heat storage media in solar thermal power generation technology. More mature heat transfer and heat storage medium.
  • the outstanding advantages of the nitrate molten salt system are that the raw materials are widely available, the price is low, the corrosion is small, and generally does not thermally decompose below 50 CTC, so the molten salt of nitric acid has great advantages compared with other molten salts.
  • the heat transfer and heat storage medium used in foreign solar thermal power stations is mainly a binary nitrate system (40% KNO 3 -60 % NaNO 3 ) and a ternary nitrate system (KN0 3 -NaN0 3 - NaN0 2 ).
  • the binary nitrate system has an operating temperature range of 260 - 565 ° C.
  • the upper limit temperature is higher, but the melting point is higher, resulting in excessive maintenance costs for cloud cover.
  • the nitrate molten salt system has the disadvantages of less heat of dissolution and low thermal conductivity, so that local overheating is likely to occur during use.
  • the binary nitrate molten salt system commonly used in China is 55 % KN0 3 -45 % NaN0 2 , and its melting point is as low as 132 ° C, which reduces the maintenance cost, but the upper limit use temperature also decreases accordingly.
  • the ternary nitrate system has a lower melting point and is ideal, but the upper limit operating temperature is lower, and the heat of dissolution is smaller and the thermal conductivity is lower.
  • the polybasic nitrate molten salt has a low melting point, but the upper limit use temperature is low.
  • Chinese Patent No. 201110425668.7 discloses a KN0 3 -NaN0 3 -Ca (N0 3 ) 2 system having an operating temperature range of 180-550 ° C, and its melting point is greatly reduced as compared with the binary nitrate system. Reduced maintenance costs.
  • calcium nitrate has poor thermal stability and decomposes when heated to 132 °C. Oxidizing, heating and releasing oxygen, burning and explosion in the presence of organic matter, sulfur, etc.
  • Cikon patent application 00111406.9 discloses a LiN03-KN03-NaN0 3 -NaN0 2 system with an operating temperature range of 250-550 ° C.
  • the upper limit operating temperature of this system is higher than that of the ternary nitrate system, reaching 550 ° C, but The lower limit operating temperature is also increased, resulting in an increase in cloud cover maintenance cost, and the addition of LiN0 3 increases corrosion and increases cost.
  • 007588694B1 discloses a LiN0 3 -KN0 3 -NaN0 3 -Ca (N0 3 ) 2 system having a melting point lower than 100 ° C and an upper limit use temperature higher than 500 ° C, but the addition of LiN 0 3 increases the molten salt. Corrosion and cost.
  • the raw materials disclosed in the prior art which can be used to improve the performance of the heat transfer and heat storage medium are mostly added with lithium nitrate, calcium nitrate, or a lithium-containing carbonic acid as disclosed in Chinese Patent No. 200910037348.7, as reported in the above literature.
  • Molten salt system Na 2 C0 3 , K 2 C0 3 , NaCl, Li 2 C0 3
  • the additives used sodium chloride and lithium carbonate effectively maintain the high safe upper temperature limit of the system, and the melting point is reduced to 390 ° C .
  • such a melting point is still high, which is likely to cause blockage of pipelines or excessive maintenance costs. How to effectively reduce the melting point of carbonated molten salt becomes an important direction of solar thermal power generation.
  • Quartz sand is a kind of ceramic material. Its unique molecular chain structure, crystal shape and lattice change law make it have the advantages of high temperature resistance, small thermal expansion coefficient, high insulation, oxidation resistance and chemical corrosion resistance.
  • the product plays an increasingly important role, and is often used as a raw material for the manufacture of glass, refractory materials, smelting ferrosilicon, metallurgical flux, ceramic abrasive materials, and casting; and is also widely selected as an industrial regenerator. So far, no reports have been made of adding quartz sand to molten salt as a heat transfer and heat storage medium for industrial energy storage and solar high temperature heat utilization. Similarly, no reports of graphite in industrial energy storage and solar high temperature heat utilization have been reported so far.
  • Graphite is an allotrope of elemental carbon. Each carbon atom is connected to another three carbon atoms (multiple hexagons arranged in a honeycomb shape) to form a covalent molecule by covalent bonding. Graphite has the following special properties due to its special structure:
  • High temperature resistance Graphite has a melting point of 3850 ⁇ 50°C and a boiling point of 4250°C. Even if it is burned by ultra-high temperature arc, the weight loss is small and the coefficient of thermal expansion is small. The strength of the graphite increases with increasing temperature, and at 200 CTC, the graphite strength is doubled.
  • Graphite has good chemical stability at normal temperature, and is resistant to acid, alkali and organic solvents.
  • Plasticity Graphite has good toughness and can be rolled into very thin sheets.
  • the invention provides a new heat transfer and heat storage medium and a preparation method thereof based on the blanks and requirements in the above-mentioned fields, and is the first application of quartz sand and graphite in heat transfer and heat storage medium, and obtains good performance improvement, such as heat. Stability, heat transfer performance; Moreover, the system cost and the material requirements for the heat transfer and heat storage device are reduced, and some defects existing in the conventional molten salt system are overcome.
  • the technical solution of the present invention is:
  • a heat transfer and heat storage medium compounded with quartz sand is characterized in that it is compounded by adding quartz sand to a heat transfer and heat storage molten salt system.
  • the heat transfer and heat storage molten salt system is a nitrate molten salt system and a carbonate molten salt system.
  • the heat transfer and heat storage molten salt system is a binary nitrate molten salt system, and the binary nitrate molten salt system accounts for 50 to 99% of the total weight of the heat transfer and heat storage medium, and the quartz sand accounts for the total heat transfer and heat storage medium. 1 ⁇ 50% of the weight.
  • the binary nitrate molten salt system accounts for 50-80% of the total weight of the heat transfer heat storage medium, and the quartz sand accounts for 20-50% of the total weight of the heat transfer heat storage medium.
  • the binary nitrate molten salt system accounts for 60-80% of the total weight of the heat transfer heat storage medium, and the quartz sand accounts for 20-40% of the total weight of the heat transfer heat storage medium.
  • the binary nitrate molten salt system accounts for 60-70% of the total weight of the heat transfer heat storage medium, and the quartz sand accounts for 30-40% of the total weight of the heat transfer heat storage medium.
  • the binary nitrate molten salt system is a KN03-NaN03 system: wherein potassium nitrate: 30-60 parts; sodium nitrate: 30-60 parts.
  • the binary nitrate molten salt system is a KN0 3 -NaN0 2 system: wherein potassium nitrate: 30-60 parts; sodium nitrite: 40-70 parts.
  • the heat transfer and heat storage molten salt system is a ternary nitrate molten salt system, and the ternary nitrate molten salt system accounts for 50 to 99% of the total weight of the heat transfer and heat storage medium, and the quartz sand accounts for the total heat transfer and heat storage medium. 1 ⁇ 50% of the weight.
  • the nitric acid molten salt system accounts for 50 to 90% of the total weight of the heat transfer and heat storage medium, and the quartz sand accounts for 10 to 50% of the total weight of the heat transfer and heat storage medium.
  • the ternary nitrate molten salt system and its weight components are as follows: KN0 3 -NaN0 3 -NaN0 2 system: wherein potassium nitrate: 40-80 parts; sodium nitrate: 5-15 parts; sodium nitrite: 10-50 parts .
  • the ternary nitrate molten salt system and its weight components are as follows: KN0 3 -NaN0 3 -Ca(N0 3 ) 2 system: wherein potassium nitrate: 5-40 parts; sodium nitrate: 5-25 parts; calcium nitrate: 10 -70 servings.
  • the heat transfer and heat storage molten salt system is a multi-component nitrate molten salt system, and the multi-component nitrate molten salt system accounts for 50 to 99% of the total weight of the heat transfer and heat storage medium, and the quartz sand accounts for the total weight of the heat transfer and heat storage medium. 1 ⁇ 50%.
  • the multi-component nitrate molten salt system accounts for 50-90% of the total weight of the heat transfer heat storage medium, and the quartz sand accounts for 10-50%.
  • the polybasic nitrate molten salt system is KN0 3 -NaN0 3 -NaN0 2 -CsN0 3 system, KN0 3 -NaN0 3 -NaN0 2 -Ca(N0 3 ) 2 system, KN0 3 -NaN0 3 -NaN0 2 -LiN0 3 system , KN0 3 -NaN0 3 -CsN0 3 -Ca(N0 3 ) 2 system, KN0 3 -NaN0 3 - LiN0 3 -CsN0 3 system or KN0 3 -NaN0 3 -NaN0 2 -CsN0 3 -Ca(N0 3 ) 2 system .
  • the weight components of the KN0 3 -NaN0 3 -NaN0 2 -CsN0 3 system are as follows: potassium nitrate 40 parts - 80 parts, sodium nitrate 5 parts - 15 parts, sodium nitrite 20-50 parts, bismuth nitrate 1 part - 10 Share
  • KN0 3 -NaN0 3 -NaN0 2 -Ca(N0 3 ) 2 system The components of the KN0 3 -NaN0 3 -NaN0 2 -Ca(N0 3 ) 2 system are as follows: potassium nitrate 40 parts - 80 parts, sodium nitrate 5 parts - 15 parts, sodium nitrite 20 parts - 50 parts, nitric acid Calcium 1 part - 10 parts;
  • the components of the KN0 3 -NaN0 3 -NaN0 2 -LiN0 3 system are as follows: potassium nitrate 40 parts - 80 parts, sodium nitrate 5 parts - 15 parts, sodium nitrite 20 parts - 50 parts; lithium nitrate 1 part - 10 Share
  • KN0 3 -NaN0 3 -CsN0 3 -Ca(N0 3 ) 2 system The components of the KN0 3 -NaN0 3 -CsN0 3 -Ca(N0 3 ) 2 system are as follows: potassium nitrate 40 parts - 80 parts, sodium nitrate 5 parts - 15 parts, lanthanum nitrate 20 parts - 50 parts, calcium nitrate 1 10 parts;
  • KN0 3 -NaN0 3 -LiN0 3 -CsN0 3 system The components of the KN0 3 -NaN0 3 -LiN0 3 -CsN0 3 system are as follows: potassium nitrate 40 parts - 80 parts, sodium nitrate 5 parts - 15 parts, lithium nitrate 20 parts - 50 parts, lanthanum nitrate 1 part - 10 parts ;
  • KN0 3 -NaN0 3 -NaN0 2 -CsN0 3 -Ca(N0 3 ) 2 are as follows: potassium nitrate 40 parts - 80 parts, sodium nitrate 5 parts - 15 parts, sodium nitrite 10 parts - 50 parts, 10 parts to 30 parts of cerium nitrate and 10 parts to 30 parts of calcium nitrate.
  • the heat transfer and heat storage molten salt system is a carbonate molten salt system: K 2 C0 3 -Na 2 C0 3 .
  • the weight component in the K 2 C0 3 -Na 2 CO system is 30-60 parts of potassium carbonate and 30-60 parts of sodium carbonate.
  • the heat transfer and heat storage molten salt system is a carbonate molten salt system: K 2 C0 3 -N a2 C0 3 -NaCl-Li 2 C0 3 system, the K 2 C0 3 -Na 2 C0 3 -NaCl-Li 2 C0
  • the weight components in the system 3 are: potassium carbonate: 20-60 parts, sodium carbonate: 20-40 parts, lithium carbonate: 10-20 parts, sodium chloride: 5-10 parts.
  • the proportion of the quartz sand in the heat transfer and heat storage medium is 1 to 50%;
  • the proportion of the quartz sand in the heat transfer and heat storage medium is 10 to 40%;
  • the proportion of the quartz sand in the heat transfer and heat storage medium is 20 to 45%;
  • the proportion of the quartz sand in the heat transfer and heat storage medium is 30 to 40%.
  • a heat transfer and heat storage medium composited with graphite is characterized by: composite graphite in a heat transfer and heat storage molten salt system.
  • a preparation process for preparing any of the above heat transfer and heat storage media characterized in that the following molten salt preparation device is used: the device comprises a heat source device, a molten salt can (2) with a sandwich, a jet mill dryer (3), Granulation device (5-1), cooling device (5-2) and output device;
  • the heat source device includes a heat carrier carrying cavity, and the heat carrier carrying cavity is connected to the interlayer of the molten salt tank (2) through a heat carrier pipe (20-1);
  • the molten salt tank (2), the jet mill dryer (3), the granulation device (5-1), the cooling device (5-2), and the output device Between the molten salt pipe, the molten salt pipe extends from the lower end of the molten salt tank (2) and communicates with the upper end of the jet mill dryer (3); the lower end of the jet mill dryer (3) Connected to the heat exchanger (4);
  • the heat source device refers to a solar heat collecting system (9), a mobile electric heat tracing (10) or a solar energy collecting system (9) and a mobile electric heat tracing (10) that are independently controlled and connected in parallel;
  • the uniformly heated molten salt is pumped into the jet mill drier (3), subjected to jet milling and drying to obtain a quartz sand/graphite composite molten salt heat transfer and heat storage medium, which is then granulated and cooled and output by the output device.
  • the heat carrier pipe (20-1) between the solar heat collecting system (9) and the molten salt tank is set to two independently controlled ones, one of which is provided with a high temperature storage tank (1);
  • a heat carrier pump (19) is disposed between the storage tank (1) and the sandwiched molten salt tank (2).
  • a high temperature molten salt pump (14) is disposed on the molten salt pipe between the sandwiched molten salt tank (2) and the jet mill dryer (3).
  • the bottom of the interlayer cavity of the sandwiched molten salt tank (2) is in communication with the heat exchanger (4) through a length of heat carrier conduit (20-2).
  • the heat exchanger (4) is in communication with the heat source device via a length of heat carrier conduit (20-3), and the heat carrier conduit (20-3) is provided with a cryogenic storage tank (18),
  • the heat carrier tubes (20), (17) are disposed on the heat carrier tubes (20-3) at both ends of the cryogenic storage tank (18).
  • the molten salt tank (2) further includes a stirring device (11) and a feed port (12).
  • the output device in turn comprises a silo (6), a packaging device (7) and/or a storage device (8).
  • At least one heat carrier pump is mounted on any one of the heat carrier tubes.
  • a molten salt preparation apparatus employed in any of the above methods.
  • the present invention is the first composite material using quartz sand or graphite as a molten salt.
  • Quartz sand is a hard, wear-resistant chemically stable silicate mineral whose main component is Si0 2 . Minerals often contain small amounts of impurity components such as Fe 2 O 3 , A1 2 0 3 , CaO, MgO, Na 2 0 Wait. It has a melting point of about 1723 ° C and a boiling point of about 2230 ° C. It has good resistance to high temperature, oxidation and chemical corrosion.
  • the quartz sand used in the present invention may be an ordinary quartz sand having a silica content of more than 75%.
  • the experiment proves that the heat transfer and heat storage medium prepared by adding quartz sand to the molten salt system of nitrate and the carbonate molten salt system has low industrial cost, little corrosiveness to the heat storage system, and is compared with the original molten salt system.
  • the heat transfer and heat storage medium prepared by the invention not only has the heat transfer performance of the original molten salt system, but also improves the thermal stability and the upper limit use temperature, and the freezing point of the molten salt does not substantially change.
  • the molten salt heat transfer and heat storage medium prepared by the invention has large latent heat of phase change, high energy storage density, low requirement on size and energy of the heat storage system, high energy utilization rate and good energy saving effect.
  • quartz sand accounts for 1 to 50%, and the higher the quartz sand content, the more obvious the cost reduction; in this range, the upper limit temperature of the molten salt can be ensured, and the melting point is not increased, and the introduction is The finer the grain size of the quartz sand, the more uniform the heat transfer of the system.
  • the loss rate is significantly reduced after being kept at 800 ° C for 30 hours compared with the original binary carbonate, indicating that the heat is stable.
  • the melting point is reduced to 540 degrees Celsius, which is wider than the original operating temperature range, and the latent heat of phase change is increased; on the other hand, quartz sand is cheaper than chloride, as this
  • the raw materials of the lossy materials will greatly reduce the cost in the field of solar thermal power generation and industrial energy storage.
  • the loss rate is significantly decreased after maintaining at 850 ° C for 30 hours compared with the original system, indicating that the thermal stability is improved.
  • the results show that the melting point drops to about 350-400 degrees Celsius, which is wider than the original operating temperature range, and the latent heat of phase change increases.
  • the addition of quartz sand significantly reduces the overall system. Raw material costs.
  • the invention adopts quartz sand to modify the heat transfer and heat storage molten salt system, thereby reducing the raw material cost as a whole.
  • the key characteristics of the original system are not impaired, and the thermal stability of the original system is improved, the latent heat of phase change is improved, and the temperature range of use is wider. It can be widely used in the solar thermal power generation industry and is conducive to the development of the industry.
  • the invention also provides a technical scheme for modifying the heat transfer and heat storage molten salt system by using graphite, and has the following special properties due to the special structure of graphite: high temperature resistance, electrical conductivity, thermal conductivity, lubricity, chemical stability, The thermal shock resistance of the graphite-provided heat transfer medium provided by the present invention is remarkably improved in terms of thermal stability and heat transfer performance.
  • the melting point referred to in the present invention means a temperature which is detected by a differential scanner under normal pressure during heating.
  • the present invention also provides a process for preparing a carbonate molten salt of the present invention in a scale, the steps of which depend on a set of equipment proposed by the present invention, and the innovations and advantages of the set of processes and equipment are as follows:
  • the heat source device provides the energy required for heating, and the heat source device can select a mobile electric heat tracing or solar heat collecting. If it is in the material site, such as solar energy thermal power station, it can directly use the concentrated solar energy, environmental protection and energy saving.
  • the heat carrier high temperature heat transfer oil or molten salt or superheated steam
  • the heat exchanger for heating required heat
  • the air makes full use of the residual heat of the heat carrier after the molten salt can is used. Overall, the thermal energy utilization rate of the process is improved.
  • the heat source device of the present invention provides the following three solutions:
  • Solution 1 uses the heat provided by the concentrated solar energy as a heat source, and is energy-saving and environmentally friendly. There are four ways to provide heat: trough, tower, dish, linear Fresnel solar thermal power generation mirror field solar energy. The trough and tower are preferred from the standpoint of cost and technical maturity.
  • Method 1 The trough mirror field of photothermal power generation is selected as the way of collecting solar energy, and the molten salt tank is directly heated by the high temperature heat carrier in the heat collecting tube.
  • the common high-temperature heat carriers are high-temperature molten salt, heat-conducting oil, and superheated steam, and heat-transfer oil is preferred in the trough mirror field.
  • Method 2 The tower mirror field of the photothermal power generation is selected as a way of collecting solar energy, and the molten salt tank is directly heated by the high temperature heat carrier in the heat absorber.
  • the common high-temperature heat carriers are high-temperature molten salt, heat-conducting oil, and superheated steam, and molten salt is preferred in the tower mirror field.
  • the mobile electric heating can also be used to provide a heat source.
  • the mobile electric heating is different from the traditional winding electric heating cable, and the maintenance is more convenient and simple.
  • Solution 3 The solar collector system and the mobile electric heat tracing are independently controlled and used in parallel, and the two can form complementary functions. For example, when the solar radiation is insufficient, the electric heat tracing can be used to supplement.
  • the heat of the hot air entering the jet pulverizer is derived from the residual heat of the heat carrier in the molten salt tank interlayer, and the maximum efficiency is utilized.
  • the temperature and pressure of the molten salt tank are controllable.
  • the final product particles are fine and uniform.
  • Figure 1 is a schematic view showing the structure of a molten salt preparation apparatus used in the process of the present invention; Among them, 1-high temperature storage tank, 2-melting salt tank, 3-air pulverizing dryer, 4 heat exchanger, 5-1 granulator, 5-2 cooling device, 6- silo, 7-packing device, 8 -Storage device, 9-Solar heat collector system, 10-mobile electric heat tracing, 11-stirring device, 12-feed port, 13-interlayer cavity, 14-high temperature molten salt pump, 15-blower, 16, 17 , 18-heat carrier pump, 18-low temperature storage tank, 20-1, 20-2, 20-3-heat carrier piping.
  • Potassium carbonate, sodium carbonate, sodium chloride, lithium chloride, industrial grade, general chemical companies can buy.
  • the preparation process of the heat transfer and heat storage medium combined with quartz sand/graphite of the invention has two options:
  • Step 1 Proportionally consists of a molten salt system, placed in a vacuum heating furnace to remove degassing and water to form a molten state, and heated at a temperature of 50-100 ° C above the molten salt phase transition temperature.
  • Step 2 Add quartz sand/graphite to the molten salt system in step (1), magnetically stir the molten mixture for 0.5-lh, soak the ultrasonic for 0.5-2h, and naturally cool to obtain a uniform and stable quartz sand/graphite composite. Molten salt.
  • molten salt preparation equipment the equipment includes a heat source device, a molten salt tank (2) with a sandwich inner cavity (13), and an air flow. a pulverizing dryer (3), a granulator (5-1), a cooling device (5-2), and an output device;
  • the raw material of the molten salt system is added to the molten salt tank (2) with the interlayer, and the heat source device is heated to the molten state, and then the quartz sand/graphite is added in proportion, and the heating is continued to the molten salt system.
  • the uniformly heated molten salt is pumped into the jet mill drier (3), subjected to jet milling and drying to obtain a quartz sand/graphite composite molten salt heat transfer and heat storage medium, which is then granulated and cooled and output by the output device.
  • the heat source device includes a heat carrier carrying cavity, and the heat carrier carrying cavity is communicated with the interlayer inner cavity (13) through a hot carrier pipe (20-1);
  • the molten salt tank (2), the jet mill dryer (3), the granulating device (5-1), the cooling device (5-2) and the output device are communicated through a molten salt pipe, the molten salt pipe Extending from the lower end of the molten salt tank (2) and communicating with the upper end of the jet mill dryer (3); the lower end of the jet mill dryer (3) is connected to the heat exchanger (4);
  • the molten salt system is drawn from above into the jet pulverizer, while hot air is blown into the dryer from the bottom of the jet pulverizer, both It is a reverse way.
  • Purpose To make the molten salt mixture system of the liquid phase form a dry and uniform powder directly after passing through the airflow pulverizer, which is convenient for packaging and sale. On the other hand, the performance is uniform when used;
  • the heat source device refers to a solar heat collecting system (9), a mobile electric heat tracing (10) or a solar heat collecting system (9) and a mobile electric heat tracing (10) that are independently controlled and connected in parallel; the heat source device in the device It may be a separate solar collector system 9 or a separate mobile electric heat tracing, or a solar collector system (9) and a mobile electric heat tracing (10) that are independently controlled and connected in parallel.
  • the heat carrier pipe (20-1) between the solar heat collecting system (9) and the molten salt tank is set to two independently controlled ones, one of which is provided with a high temperature storage tank (1)
  • a valve is disposed between the thermal system 9 and the high temperature storage tank 1 for controlling the flow of the heat carrier in the solar heat collecting system 9 to the high temperature storage tank 1; when the valve is closed, the solar heat collecting system 9 or
  • the mobile electric heat tracing 10 directly heats the heat carrier and heats the molten salt tank 2 to prepare a high temperature molten salt; when the energy is sufficient or the molten salt tank does not need to be heated, the solar heat collecting system and the high temperature storage tank 1 can be opened.
  • the valve, the heat carrier heated by the solar collector system can be stored through the pipeline to the high temperature storage tank, and when heated, the heat carrier pump (19) can be pumped into the interlayer cavity (13) to heat the molten salt tank.
  • the heat carrier pump (19) can be pumped into the interlayer cavity (13) to heat the molten salt tank.
  • a high temperature molten salt pump (14) is disposed on the molten salt pipe between the molten salt tank (2) and the jet mill dryer (3). It is used to pump the heated molten salt into a jet mill dryer.
  • the bottom of the interlayer inner chamber (13) of the sandwiched molten salt tank (2) is in communication with the heat exchanger (4) through a length of heat carrier conduit (20-2).
  • the section of heat carrier conduit (20-2) is used to direct the heat carrier in the interlayer cavity (13) to the heat exchanger (4) for heating the hot air required in the apparatus.
  • the residual heat of the heat carrier in the inner cavity (13) of the interlayer is reused, which is energy-saving and environmentally friendly.
  • the heat exchanger (4) is in communication with the heat source device via a length of heat carrier conduit (20-3), and the heat carrier conduit (20-3) is provided with a low temperature storage tank (18).
  • Heat carrier pumps (16), (17) are disposed on the heat carrier tubes (20-3) at both ends of the cryogenic storage tank (18). After being cooled by the heat carrier that has run out of heat in the heat exchanger, it is pumped through the heat carrier pump (16) on the heat carrier pipe (20-3) to the cryogenic storage tank, and sent back to the heat carrier pump (17). It is recycled in the heat source unit.
  • the molten salt tank (2) further includes a stirring device (11) and a feed port (12).
  • the output device comprises, in order, a silo (6), a packaging device (7) and/or a storage device (8).
  • At least one heat carrier pump is disposed in each of the sections of the heat carrier.
  • valves are provided on each of the sections of the apparatus for controlling the flow and flow of material in the pipeline.
  • the valve on the heat carrier conduit between the heat source device and the sandwiched molten salt canister controls the heating temperature by controlling the delivery rate and speed of the heat carrier, which itself has a pressure control device.
  • Step 2 Disperse the quartz sand into the molten binary nitrate molten salt system under stirring conditions, continue stirring for l-2h, and the mixture is gelatinous.
  • the added quartz sand (specification 100 mesh) is graded according to the following scale:
  • Group 1 Quartz sand accounts for 1% of the three quartz sand composite binary nitric acid molten salt heat transfer and heat storage medium, and the first to third products are obtained.
  • Group 2 Quartz sand accounts for 10% of the three quartz sand composite binary nitric acid molten salt heat transfer and heat storage medium, and the fourth to sixth products are obtained.
  • Group 3 Quartz sand accounts for 20% of the three kinds of quartz sand composite binary nitrate molten salt heat transfer and heat storage medium, and the 7th to 9th products are obtained.
  • Group 4 Quartz sand accounts for 30% of the three quartz sand composite binary nitric acid molten salt heat transfer and heat storage medium
  • the 10th to 12th f- group 5 Quartz sand in three quartz sand composite binary nitric acid 40% of the molten salt heat transfer and heat storage medium
  • the 13th to 15th production f group 6 Quartz sand accounts for 50% of the three quartz sand composite binary nitric acid molten salt heat transfer and heat storage medium
  • the 16th ⁇ 18 controls for each product are the binary nitrate salts of the product.
  • Step 3 Phase change latent heat test and melting point test:
  • the heat stability test was carried out on 18 kinds of heat transfer heat storage medium and three kinds of control binary nitrate molten salt.
  • the test was carried out by gravimetric method: The 18 kinds of molten salts obtained in Examples 1 to 3 were separately placed in a crucible made of nickel, and placed in a temperature controlled furnace for heating. The experiment was started from room temperature, and the experiment was taken at intervals. Analyze the balance to weigh. If the weight of the sample is no longer reduced within a certain temperature range, increase the temperature of the temperature control furnace. Then, the experiment ⁇ is taken out at regular intervals for weighing, and the temperature is continued after another steady state.
  • the stability temperature limits of the four control binary nitric acid systems are all 550 ° C, heating at 550 ° C for 100 hours, the loss rate can reach 10%; heating for 30 hours, the loss rate is 5%. , 710 heat 100 hours, the loss rate can reach 25%, heating for 30 hours, the loss rate is 13%.
  • the third group ⁇ 3.5 ⁇ 6. 5%
  • the fourth group ⁇ 5.5 ⁇ 13.0
  • the sixth group ⁇ 5.1 ⁇ 11 shows that at 71 CTC, the addition of very little quartz sand enables the thermal stability of each group of products to be improved relative to the illumination.
  • Example 4 ⁇ 7 Adding Quartz Sand to Binary Nitrate System KN0 3 -NaN0 2 to Prepare Heat Storage and Heat Transfer Medium
  • Step 1 According to the formula listed in Table 5, prepare the material of the binary nitrate molten salt system, put it into the reaction kettle, heat and stir to completely melt the solid, then keep it for 0.5-lh, and the heating temperature is above the molten salt phase transition temperature. -120 ° C.
  • Step 2 Disperse the quartz sand into the molten binary nitrate molten salt system under stirring conditions, continue stirring for l-2h, and the mixture is gelatinous.
  • the added quartz sand (specification 100 mesh) was carried out according to the following scale: Group 1: Quartz sand accounts for 1% of the four quartz sand composite binary nitric acid molten salt heat transfer and heat storage medium, and the first to fourth products are obtained. Group 2: Quartz sand accounts for 10% of the four quartz sand composite binary nitric acid molten salt heat transfer and heat storage medium, and the 5th to 8th products are obtained. Group 3: Quartz sand accounts for 20% of the four quartz sand composite binary nitric acid molten salt heat transfer and heat storage medium, and the 9th to 12th products are obtained.
  • Group 4 Quartz sand in four quartz sand composite binary nitric acid The molten salt heat transfer and heat storage medium accounts for 30%, and the 13th to 16th production n n group 5: quartz sand accounts for 40% of the four quartz sand composite binary nitrate molten salt heat transfer and heat storage medium. 17 ⁇ 20 production group 6: Quartz sand accounts for 50% of the four quartz sand composite binary nitric acid molten salt heat transfer and heat storage medium, and the 21st to 24th production n n each product is the corresponding product The binary nitrate molten salt.
  • Step 3 Phase change latent heat test and melting point test:
  • the melting points of the first to fourth groups of products were decreased; the melting points of the fifth and sixth groups were slightly increased.
  • thermal stability tests were carried out on 24 heat transfer and heat storage media and 4 control binary nitrate molten salts.
  • the test was carried out by gravimetric method: The 24 kinds of molten salts obtained in Examples 5 to 8 were separately placed in a crucible made of nickel, and placed in a temperature controlled furnace for heating. The experiment was started from room temperature, and the experiment was taken at intervals. Analyze the balance to weigh. If the weight of the sample is no longer reduced within a certain temperature range, increase the temperature of the temperature control furnace. Then, the experiment ⁇ is taken out at regular intervals for weighing, and the temperature is continued after another steady state.
  • the stability temperature limits of the four control binary nitric acid systems are both 500 ° C, heating at 500 ° C for 100 hours, the loss rate can reach 12%; heating for 30 hours, the loss rate is 5%. , heating at 600 ° C for 100 hours, the loss rate can reach 22%; heating for 30 hours, the loss rate of 12%.
  • quartz sand at 50 CTC can significantly improve the thermal stability of each group of products relative to the control.
  • Example 8 ⁇ 11 Preparation of heat storage heat transfer medium by adding quartz sand to ternary nitrate system KN0 3 -NaN0 3 -NaN0 2
  • Step 1 According to the formula listed in Table 9, prepare the material of the ternary nitrate molten salt system, put it into the reaction kettle, heat and stir to completely melt the solid, and then keep the temperature for 0.5-lh, the heating temperature is above the melting salt phase transition temperature 50 -100 ° C.
  • Step 2 Disperse the quartz sand into the molten ternary nitrate molten salt system under stirring conditions, continue stirring for l-2h, and the mixture is gelatinous.
  • the added quartz sand (specification 100 mesh) is graded according to the following scale:
  • the first group Quartz sand accounts for 1% of the four quartz sand composite ternary nitrate molten salt heat transfer and heat storage medium, and the first to fourth products are obtained.
  • the second group Quartz sand accounts for 10% of the four quartz sand composite ternary nitrate molten salt heat transfer and heat storage medium, and the fifth to eighth production
  • the third group Quartz sand accounts for 25% of the four quartz sand composite ternary nitrate molten salt heat transfer and heat storage medium, and the 9th to 12th production Group 4: Quartz sand accounts for 40% of the four quartz sand composite ternary nitrate molten salt heat transfer and heat storage medium, and the 13th to 16th mouth
  • Group 5 Quartz sand accounts for 50% of the four quartz sand composite ternary nitrate molten salt heat transfer and heat storage medium, and the 17th to 20th mouth
  • Step 3 Phase change latent heat test and melting point test.
  • test results show that the latent heat of phase change is significantly increased compared with the control; the melting point of the first to third groups is basically unchanged, and the melting points of the fourth and fifth groups are slightly increased.
  • the heat stability test was carried out on 20 kinds of heat transfer and heat storage medium and the control ternary nitrate molten salt.
  • the test was carried out by gravimetric method: The 20 kinds of molten salts obtained in Examples 8-11 were separately placed in a crucible made of nickel, placed in a temperature controlled furnace for heating, and the experiment was started from room temperature, and the experiment was taken at intervals. Analyze the balance to weigh. If the weight of the sample is no longer reduced within a certain temperature range, increase the temperature of the temperature control furnace. Then, the experiment ⁇ is taken out at regular intervals for weighing, and the temperature is continued after another steady state.
  • the stable temperature limit of the control ternary nitric acid system is 500 ° C, heating at 500 ° C for 100 hours, the loss rate can reach 25%, heating for 30 hours, the loss rate is 10%. Heating at 600 ° C for 100 hours, the loss rate can reach 30%, heating for 30 hours, the loss rate is 15%. Heating at 700 ° C °C for 100 hours, the loss rate can reach 35%, heating for 30 hours, the loss rate is 24%.
  • Product group number The first group 15-20% 25-30%
  • quartz sand at 600 ° C and 700 ° C can improve the thermal stability of each group of products relative to the illumination.
  • Example 12 ⁇ 14 Preparation of heat storage heat transfer medium by adding quartz sand to ternary nitrate system KN0 3 -NaN0 3 -Ca (N0 3 ) Step 1.2 Preparation of quartz sand composite ternary nitrate molten salt according to the formula listed in Table 12 The method is the same as the method of steps 1 and 2 of Examples 8 to 11.
  • the added quartz sand is carried out according to the gradient:
  • the first group Quartz sand accounts for 1% of the three quartz sand composite ternary nitrate molten salt heat transfer and heat storage medium, and the first to third products are obtained.
  • the second group Quartz sand accounts for 30% of the four quartz sand composite ternary nitrate molten salt heat transfer and heat storage medium, and the fourth to sixth production
  • the third group Quartz sand accounts for 50% of the four quartz sand composite ternary nitrate molten salt heat transfer and heat storage medium, and the 7th to 9th production
  • Step 3 Phase change latent heat test and melting point test.
  • test results show that the latent heat of phase change is significantly increased; compared with the control, the melting points of the first group and the second group are basically unchanged, and the melting point of the third group is improved.
  • Step 4 Thermal stability test The heat stability test was carried out on 9 kinds of heat transfer heat storage medium and control ternary nitrate molten salt.
  • the test was carried out by gravimetric method: the nine molten salts obtained in Examples 12 to 14 were separately placed in a crucible made of nickel, and placed in a temperature controlled furnace for heating. The experiment was started from a normal temperature, and the experiment was taken at intervals. Analyze the balance to weigh. If the weight of the sample is no longer reduced within a certain temperature range, increase the temperature of the temperature control furnace. Then, the experiment ⁇ is taken out at regular intervals for weighing, and the temperature is continued after another steady state.
  • the stable temperature limit of the control ternary nitric acid system is 550 ° C, heating at 550 ° C for 30 hours, the loss rate is about 3%, the loss rate is about 6% when heated for 50 hours; the heating is 650 ° C for 30 hours, the loss rate is about 5%, the loss rate is about 10% when heated for 50 hours; the temperature is 750 ° C for 30 hours, the loss rate is about 7%, and the loss rate is about 15% when heated for 50 hours;
  • the loss rate is about 7%, and the heat loss rate is about 12 at 50 hours.
  • the loss rate of the product of the present invention at 75 CTC is comparable to that of the control at 55 CTC, indicating that the product of the present invention has better thermal stability and can be stably operated at 75 CTC for a longer period of time.
  • Example 15 ⁇ 17 Preparation of heat storage heat transfer medium by adding quartz sand to KN0 3 -NaN0 3 -NaN0 2 -CsN0 3 1. Preparation of quartz sand composite multi-nitrate molten salt products 1 ⁇ 3:
  • quartz sand (100 mesh) is dispersed into the molten polybasic nitrate molten salt system, and the molten mixture is stirred for 1-2 hours to obtain a quartz sand composite polynitrate molten salt heat transfer and heat storage medium. Quartz sand accounts for 1%, 20%, and 50% of products 1 ⁇ 3, respectively. Table 15. Formulation of the polynitrate system in each example
  • 26 40 parts of potassium nitrate, 15 parts of sodium nitrate, 50 parts of cerium nitrate, 1 part of calcium nitrate;
  • the prepared heat transfer and heat storage medium and the control polybasic nitrate molten salt were tested for thermal stability.
  • the test was carried out by gravimetric method: the three molten salts obtained in Examples 15 to 17 were separately placed in a crucible made of nickel, and placed in a temperature controlled furnace for heating. The experiment was started from a normal temperature, and the experiment was taken at intervals. Analyze the balance to weigh. If the weight of the sample is no longer reduced within a certain temperature range, increase the temperature of the temperature control furnace. Then, the experiment ⁇ is taken out at regular intervals for weighing, and then continues to warm up after another steady state.
  • Quartz sand composite multi-nitrate molten salt product 1 ⁇ 3 molten salt is kept at 600 °C for 120 hours, and the loss rate is less than 1%;
  • the loss rates of the three products were about 20%, 3%, and 1%, respectively.
  • the comparison is the molten salt of three polybasic nitric acid systems without quartz sand (the system corresponding to No. 15-17 in Table 15), and the loss rate at 600 °C for 30 hours is about 8%, but at 700. Significant losses occurred at °C, running to 30 hours, and the loss rate was 25%.
  • Quartz sand composite multi-nitrate molten salt product 1 ⁇ 3 phase change latent heat test and melting point test.
  • test results show that the latent heat of phase change is significantly increased compared with the control; the melting points of products 1 and 2 are basically unchanged, and the melting point of product 3 is slightly increased.
  • Example 18 ⁇ 20 Preparation of a heat storage heat transfer medium by adding quartz sand to a multi-nitrate system KN0 3 -NaN0 3 -NaN0 2 -Ca(N0 3 ) 2
  • the materials constituting the polybasic nitrate molten salt system were prepared according to the formulations listed in Table 15.
  • the preparation methods and detection methods of products 4 to 6 are exactly the same as those of Examples 15 to 17, quartz sand (100 mesh) accounted for 10%, 25%, and 40%, respectively; the control did not contain quartz sand, and the examples 15 to 17 in Table 15 Corresponding system.
  • Example 21 ⁇ 23 Multi-nitrate system KN0 3 -NaN0 3 -NaN0 2 -LiN0 3 Add quartz sand to prepare heat storage heat transfer medium According to the formula listed in Table 15, prepare the material of the multi-component nitrate molten salt system.
  • the preparation method and detection method are exactly the same as those in Examples 15-17.
  • Example 24 ⁇ 26 Preparation of a heat storage heat transfer medium by adding quartz sand to a multi-nitrate system KN0 3 -NaN0 3 -CsN0 3 -Ca(N0 3 ) 2
  • the preparation method and detection method of the products 10 ⁇ 12 are completely the same as those of the examples 15 ⁇ 17.
  • Quartz sand (100 mesh) accounted for 10%, 25%, and 45%, respectively; the control did not contain quartz sand, which was the system corresponding to Examples 25-27 in Table 15.
  • Example 27 ⁇ 32 Adding Quartz Sand to Other Multi-Nitrate System to Prepare Heat Storage and Heat Transfer Medium
  • the preparation methods and detection methods of the products 13 to 18 are completely the same as those of the examples 16 to 18.
  • the proportions of the quartz sands (100 meshes) of the three formulations of each of the multi-component nitrate molten salt systems are: 15%, 25%, 40 %;
  • the control does not contain quartz sand and is the system corresponding to Examples 27 to 32 in Table 15.
  • the loss rate of the six products prepared by the present invention was as high as 11% and 2.5% 1% after being kept at 70 CTC for 30 hours, which was significantly lower than that of the control.
  • the heat transfer performance of the molten salt of nitric acid is increased, and the upper limit use temperature of the molten salt of the polybasic nitrate is increased; the use temperature range is wider and the thermal stability is good.
  • the latent heat of phase change is large, and the energy storage density is high, which reduces the size and energy requirements of the heat storage system, and has high energy utilization rate and good energy saving effect.
  • the thermal conductivity of the molten salt heat transfer and heat storage medium prepared by the invention is greatly increased, and the disadvantages of poor thermal conductivity of the molten salt of the nitric acid and easy local overheating are overcome, and can be widely used in the field of solar thermal power generation technology.
  • Example 33 ⁇ 36 Quartz sand-dicarbonate molten salt composite system
  • Step 1 According to the formula listed in Table 16, prepare the material of the binary carbonate molten salt system, put it into the reaction kettle, heat and stir to completely melt the solid, and then keep the temperature for 0.5-lh, the heating temperature is above the molten salt phase transition temperature 80 -120 ° C.
  • Step 2 Under stirring conditions, disperse the quartz sand into the molten binary carbonate molten salt system according to the following experimental design, and continue stirring for l-2h to obtain quartz sand composite carbonate molten salt, which is gelatinous.
  • quartz sand (specification 100 mesh) added to the experimental design of the present invention was carried out according to the following ratio gradient:
  • Group 1 Quartz sand accounts for 1% of the four quartz sand composite binary carbonate molten salt heat transfer and heat storage medium, and the first to fourth products are obtained.
  • Group 2 Quartz sand accounts for 10% of the four quartz sand composite binary carbonate molten salt heat transfer and heat storage medium, and the 5th to 8th products are obtained.
  • Group 3 Quartz sand accounts for 20% of the four quartz sand composite binary carbonate molten salt heat transfer and heat storage medium, and the 9th to 12th products are obtained.
  • Group 4 Quartz sand accounts for 30% of the four quartz sand composite binary carbonate molten salt heat transfer and heat storage medium, and the 13th to 16th products are obtained.
  • Group 5 Quartz sand accounts for 40% of the four quartz sand composite binary carbonate molten salt heat transfer and heat storage medium, and the 17th to 20th products are obtained.
  • Group 6 Quartz sand accounts for 50% of the four quartz sand composite binary carbonate molten salt heat transfer and heat storage medium, and the 21st to 24th products are obtained.
  • Step 3 Phase change latent heat test and melting point test:
  • the melting points of the first to fourth groups were all lowered, and the melting point was between 530 and 560 degrees Celsius; the melting points of the fifth and sixth groups were slightly increased at around 600 degrees Celsius.
  • the test was carried out by gravimetric method: The 24 kinds of molten salts obtained in Examples 33-36 were separately placed in a crucible made of nickel, placed in a temperature controlled furnace for heating, and the experiment was started from room temperature, and the experiment was taken at intervals. Analyze the balance to weigh. If the weight of the sample is no longer reduced within a certain temperature range, increase the temperature of the temperature control furnace. Then, the experiment is taken out at regular intervals for weighing, and the temperature is continued after another steady state.
  • the lithium carbonate containing molten salt system is shown in Table 18.
  • Step 1 According to the formula listed in Table 18, prepare the material containing the lithium carbonate molten salt system, put it into the reaction kettle and stir it to melt the solid completely, then keep it for 0.5-lh, and the heating temperature is above the molten salt phase transition temperature 80- 120 ° C.
  • Step 2 Under the stirring condition, the quartz sand is dispersed into the molten lithium carbonate molten salt system according to the proportion of the following experimental design, and stirring is continued for l-2h, and the quartz sand composite carbonate molten salt is obtained, which is gelatinous.
  • quartz sand (specification 100 mesh) added to the experimental design of the present invention was carried out according to the following ratio gradient:
  • Group 1 Quartz sand accounts for 1% of the four quartz sand composite carbonate molten salt heat transfer and heat storage medium, and the 25th to 28th products are obtained.
  • Group 2 Quartz sand accounts for 10% of the four quartz sand composite carbonate molten salt heat transfer and heat storage media, and the 29th to 32th products are obtained.
  • Group 3 Quartz sand accounts for 20% of the four quartz sand composite carbonate molten salt heat transfer and heat storage medium, and the 33rd to 36th products are obtained.
  • Group 4 Quartz sand accounts for 30% of the four quartz sand composite carbonate molten salt heat transfer and heat storage media, and the 37th to 40th products are obtained.
  • Group 5 Quartz sand accounts for 40% of the four quartz sand composite binary carbonate molten salt heat transfer and heat storage medium, and the 41st to 44th products are obtained.
  • Group 6 Quartz sand accounts for 50% of the four quartz sand composite binary carbonate molten salt heat transfer and heat storage medium, and the 45th to 48th products are obtained.
  • Step 3 Phase change latent heat test and melting point test:
  • the melting points of the first to fourth groups of products are all reduced, and the melting point is between 320 and 380 degrees Celsius;
  • the melting points of Group 5 and Group 6 products increased slightly, around 400-410 °C.
  • the test was carried out by gravimetric method: The 24 kinds of molten salts obtained in Examples 37 to 40 were separately placed in a crucible made of nickel, placed in a temperature controlled furnace for heating, and the experiment was started from room temperature, and the experiment was taken at intervals. Analyze the balance to weigh. If the weight of the sample is no longer reduced within a certain temperature range, increase the temperature of the temperature control furnace. Then, the experiment was taken out at regular intervals for weighing, and the temperature was continued after another steady state. The results show that the thermal stability of the four control lithium-containing carbonic acid systems is as follows:
  • the loss rate is about 5%
  • the loss rate is about 10%.
  • quartz sand can significantly improve the thermal stability of each group of products relative to the control.
  • Example 41 ⁇ 43 Adding graphite to the ternary nitrate system KN0 3 -NaN0 3 -Ca (N0 3 ) to prepare a heat storage heat transfer medium
  • the ternary nitrate molten salt system of Examples 12 to 14 was used in the same manner as in the first step of Examples 8 to 11.
  • the added graphite is carried out by gradient:
  • Example 41 is the first group: graphite accounts for 1% of the three quartz sand composite ternary nitrate molten salt heat transfer and heat storage medium.
  • Example 42 is the second group: Graphite accounts for 30% of the four quartz sand composite ternary nitrate molten salt heat transfer and heat storage medium, and the fourth to sixth products are obtained.
  • Example 43 is the third group: Graphite accounts for 50% of the four quartz sand composite ternary nitrate molten salt heat transfer and heat storage medium, and the 7-9th product is obtained.
  • Step 3 Phase change latent heat test and melting point test.
  • test results show that the latent heat of phase change is significantly increased; compared with the control, the melting points of the first group and the second group are basically unchanged, and the melting point of the third group is improved.
  • the thermal stability tests were carried out on 9 kinds of heat transfer heat storage medium and control ternary nitrate molten salt.
  • the test was carried out by gravimetric method: 9 kinds of molten salts were separately charged into a nickel crucible and placed in a temperature controlled furnace for heating. The experiment was started at room temperature, and the experiment was taken at regular intervals and weighed with an analytical balance. If the weight of the sample is no longer reduced within a certain temperature range, increase the temperature of the temperature control furnace. Then, the experiment was taken out at regular intervals for weighing, and the temperature was continued after another steady state.
  • the stable temperature limit of the control ternary nitric acid system is 550 ° C, heating at 550 ° C for 30 hours, the loss rate is about 3%, the loss rate is about 8% when heated for 50 hours; heating at 650 ° C for 30 hours, the loss rate is about 5.5%, the loss rate was about 12% when heated for 50 hours; the heat loss rate was about 9% at 750 ° C for 30 hours, and the loss rate was about 17% when heated for 50 hours.
  • the loss rate of the product of the present invention at 75 CTC is comparable to that of the control at 55 CTC, and the result is similar to the addition of quartz sand, and can be stably operated at 750 ° C for a long time.

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Abstract

本发明"石英砂/石墨复合熔盐传热蓄热介质及其制备方法"，涉及太阳能光热发电技术。其特征在于在现有常用传热蓄热熔盐体系中加入石英砂复合而成。所得传热蓄热介质的热稳定性普遍得以提高，使用温度范围扩大，腐蚀性降低，大大延长了设备的使用寿命。而且原料成本降低。

Description

技术领域
本发明涉及用于太阳能光热发电的蓄热传热复合介质，特别是涉及复合有石英砂或石墨的 熔盐传热蓄热介质及其制备方法。
背景技术
在工业蓄能和太阳能光热发电技术中， 目前使用的蓄热传热介质主要有空气、水、导热油、 熔融盐、钠和铝金属等。熔盐因具有广泛的使用温度范围， 低蒸汽压， 低粘度， 良好的稳定性， 低成本等诸多特性已成为太阳能光热发电技术中颇具潜力的传热蓄热介质， 成为目前应用较 多， 较为成熟的传热蓄热介质。
硝酸熔盐体系的突出优点是原料来源广泛、 价格低廉、 腐蚀性小且一般在 50CTC以下不会 热分解， 因此与其他熔盐相比， 硝酸熔盐具有很大的优势。 目前， 国外太阳能光热发电的电站 所使用的传热蓄热介质主要为二元硝酸盐体系 （40 %KNO3-60 %NaNO3 ) 和三元硝酸盐体系 (KN03-NaN03- NaN02)。
二元硝酸盐体系的工作温度范围为 260 -565°C， 上限温度较高比较理想， 但是熔点偏高， 导致云遮时的维护成本过高。硝酸熔盐体系存在溶解热较小、热导率低的缺点， 因此在使用时 容易产生局部过热。 国内通常采用的二元硝酸熔盐体系是 55 %KN03-45 %NaN02,其熔点低至 132°C， 减少了维护成本， 但是上限使用温度也相应降低。
三元硝酸盐体系的熔点较低， 比较理想， 但是上限工作温度偏低， 且溶解热较小、 热导率 较低。
其中的多元硝酸熔盐熔点低， 但是上限使用温度低。
为了解决上述问题， 中国专利 201110425668.7公开了一种 KN03-NaN03-Ca (N03) 2体系， 工作温度范围 180-550°C， 与二元硝酸盐体系相比， 其熔点大幅度降低， 减少了维护成本。 但 是硝酸钙热稳定性不好， 热至 132°C即分解。 有氧化性， 加热放出氧气， 遇有机物、 硫等即发 生燃烧和爆炸。
中国专利申请 00111406.9公开了一种 LiN03- KN03-NaN03-NaN02体系， 其工作温度范 围为 250 -550°C， 这个体系的上限工作温度比三元硝酸盐体系高， 达到 550°C， 但其下限工作 温度也被提高， 导致云遮时维护成本增大， 而且 LiN03的加入使得其腐蚀性增大， 成本增高。 美国专利 US007588694B1公开了一种 LiN03-KN03-NaN03-Ca (N03) 2体系， 其熔点低 于 100°C， 上限使用温度高于 500 °C， 但是 LiN03的加入增加了熔盐的腐蚀性和成本。
现有技术中公开的可用于改善传热蓄热介质的性能的原料多如以上文献所报道的在硝酸 熔盐体系中加入硝酸锂、 硝酸钙、 或如中国专利 200910037348.7公开的一种含锂碳酸熔盐体 系（Na2C03, K2C03, NaCl, Li2C03)， 所采用的添加剂氯化钠和碳酸锂， 有效维持体系高的安全 使用温度上限， 且熔点降低至 390°C。 但是在实际应用中， 这样的熔点还是偏高， 容易造成管 路阻塞或者维护成本过高，如何有效降低碳酸熔盐的熔点成为太阳能光热发电蓄热的一个重要 方向。
石英砂是陶瓷材料的一种， 其独特的分子链结构、 晶体形状和晶格变化规律， 使其具有耐 高温、 热膨胀系数小、 高度绝缘、 抗氧化、 耐化学腐蚀等优点， 在许多高科技产品中发挥着越 来越重要的作用， 常被用作制造玻璃、 耐火材料、 冶炼硅铁、 冶金熔剂、 陶瓷研磨材料、 铸造 的原料； 同时被大量地选做工业蓄热体。 目前为止， 没有见到将石英砂加入到熔盐中作为工业 蓄能和太阳能高温热利用领域的传热蓄热介质的报道。 同样， 目前为止， 也未见到石墨在工业 蓄能和太阳能高温热利用领域的应用报道。
石墨是元素碳的一种同素异形体，每个碳原子的周边连结著另外三个碳原子（排列方式呈 蜂巢式的多个六边形） 以共价键结合， 构成共价分子。 石墨由于其特殊结构， 而具有如下特殊 性质：
1 ) 耐高温性： 石墨的熔点为 3850±50°C， 沸点为 4250°C， 即使经超高温电弧灼烧， 重量 的损失很小， 热膨胀系数也很小。 石墨强度随温度提高而加强， 在 200CTC时， 石墨强度提高 一倍。
2) 导电、 导热性： 石墨的导电性比一般非金属矿高一百倍。 导热性超过钢、 铁、 铅等金 属材料。 导热系数随温度升高而降低， 甚至在极高的温度下， 石墨成绝热体。
3 ) 润滑性： 石墨的润滑性能取决于石墨鳞片的大小， 鳞片越大， 摩擦系数越小， 润滑性 能越好。
4)化学稳定性： 石墨在常温下有良好的化学稳定性， 能耐酸、 耐碱和耐有机溶剂的腐蚀。
5 ) 可塑性： 石墨的韧性好， 可碾成很薄的薄片。
6) 抗热震性： 石墨在常温下使用时能经受住温度的剧烈变化而不致破坏， 温度突变时， 石墨的体积变化不大， 不会产生裂纹。
发明内容
本发明基于上述领域的空白和需求，提供一种新的传热蓄热介质及其制备方法， 是石英砂 以及石墨在传热蓄热介质的首次应用，并且获得了良好的性能改进，例如热稳定性，传热性能; 而且降低了系统成本以及对传热蓄热设备的材料要求，克服了目前常用熔盐体系中存在的一些 缺陷， 本发明的技术方案是：
复合有石英砂的传热蓄热介质，其特征在于： 是通过在传热蓄热熔盐体系中加入石英砂复 合而成。
所述传热蓄热熔盐体系为硝酸熔盐体系、 碳酸熔盐体系。
所述传热蓄热熔盐体系为二元硝酸熔盐体系，所述二元硝酸熔盐体系占传热蓄热介质总重 量的 50~99%， 所述石英砂占传热蓄热介质总重量的 1~50%。
所述二元硝酸熔盐体系占传热蓄热介质总重量的 50~80%， 所述石英砂占传热蓄热介质总 重量的 20~50%。
所述二元硝酸熔盐体系占传热蓄热介质总重量的 60~80%， 所述石英砂占传热蓄热介质总 重量的 20~40%。
所述二元硝酸熔盐体系占传热蓄热介质总重量的 60~70%， 所述石英砂占传热蓄热介质总 重量的 30~40%
所述二元硝酸熔盐体系为 KN03-NaN03体系： 其中硝酸钾： 30-60份； 硝酸钠： 30-60份。 所述二元硝酸熔盐体系为 KN03-NaN02体系： 其中硝酸钾： 30-60份； 亚硝酸钠： 40-70 份。
所述传热蓄热熔盐体系为三元硝酸熔盐体系，所述三元硝酸熔盐体系占传热蓄热介质总重 量的 50~99%， 所述石英砂占传热蓄热介质总重量的 1~50%。
所述硝酸熔盐体系占传热蓄热介质总重量的 50~90%， 所述石英砂占传热蓄热介质总重量 的 10~50%。
所述三元硝酸熔盐体系及其重量组分如下： KN03-NaN03-NaN02体系：其中硝酸钾： 40-80 份； 硝酸钠： 5-15份; 亚硝酸钠： 10-50份。
所述三元硝酸熔盐体系及其重量组分如下： KN03-NaN03-Ca(N03)2体系： 其中硝酸钾： 5-40份； 硝酸钠： 5-25份； 硝酸钙： 10-70份。
所述传热蓄热熔盐体系为多元硝酸熔盐体系，所述多元硝酸熔盐体系占传热蓄热介质总重 量的 50~99%， 所述石英砂占传热蓄热介质总重量的 1~50%。
所述多元硝酸熔盐体系占传热蓄热介质总重量的 50~90 %， 石英砂占 10~50%。
所 述 多 元 硝 酸 熔 盐 体 系 为 KN03-NaN03-NaN02-CsN03 体 系 、 KN03-NaN03-NaN02-Ca(N03)2 体 系 、 KN03-NaN03-NaN02-LiN03 体 系 、 KN03-NaN03-CsN03-Ca(N03)2 体 系 、 KN03-NaN03- LiN03-CsN03 体 系 或 KN03-NaN03-NaN02-CsN03-Ca(N03)2体系。 所述 KN03-NaN03-NaN02-CsN03体系的重量组分如下： 硝酸钾 40份 -80份， 硝酸钠 5份 -15份， 亚硝酸钠 20-50份， 硝酸铯 1份 -10份；
所述 KN03-NaN03-NaN02-Ca(N03)2体系的组分如下：硝酸钾 40份 -80份，硝酸钠 5份 -15 份，； 亚硝酸钠 20份 -50份， 硝酸钙 1份 -10份；
所述 KN03-NaN03-NaN02-LiN03体系的组分如下： 硝酸钾 40份 -80份， 硝酸钠 5份 -15 份， 亚硝酸钠 20份 -50份; 硝酸锂 1份 -10份；
所述 KN03-NaN03-CsN03-Ca(N03)2体系的组分如下： 硝酸钾 40份 -80份，硝酸钠 5份 -15 份， 硝酸铯 20份 -50份， 硝酸钙 1份 -10份；
所述 KN03-NaN03- LiN03-CsN03体系的组分如下： 硝酸钾 40份 -80份， 硝酸钠 5份 -15 份， 硝酸锂 20份 -50份， 硝酸铯 1份 -10份；
所述 KN03-NaN03-NaN02-CsN03-Ca(N03)2的组分如下： 硝酸钾 40份 -80份， 硝酸钠 5份 -15份， 亚硝酸钠 10份 -50份， 硝酸铯 10份 -30份， 硝酸钙 10份 -30份。
所述传热蓄热熔盐体系为碳酸熔盐体系： K2C03-Na2C03。
所述 K2C03-Na2CO体系中的重量组分为碳酸钾 30~60份， 碳酸钠 30~60份。
所述传热蓄热熔盐体系为碳酸熔盐体系： K2C03-Na2C03-NaCl-Li2C03体系， 所述 K2C03-Na2C03-NaCl-Li2C03体系中的重量组分为： 碳酸钾： 20-60份、 碳酸钠： 20-40份、 碳 酸锂： 10-20份、 氯化钠： 5-10份。
所述石英砂在所述传热蓄热介质中所占的比例为 1~50%；
所述石英砂在所述传热蓄热介质中所占的比例为 10~40%；
所述石英砂在所述传热蓄热介质中所占的比例为 20~45%；
或所述石英砂在所述传热蓄热介质中所占的比例为 30~40%。
一种复合有石墨的传热蓄热介质， 其特征在于： 在传热蓄热熔盐体系中复合石墨而得。 所述的复合有石墨的传热蓄热介质， 所述传热蓄热熔盐体系指 KN03-NaN03-Ca(N03)2： 其中硝酸钾： 5-40份； 硝酸钠： 5-25份； 硝酸钙： 10-70份， 石墨占 1-50%.
上述任一传热蓄热介质在工业蓄能或太阳能光热发电中的用途。
用于制备上述任一传热蓄热介质的制备工艺，其特征在于采用以下熔盐制备设备： 所述设 备包括热源装置、带夹层的熔盐罐（2)、气流粉碎干燥器（3)、造粒装置（5-1 )、冷却装置（5-2) 和输出装置；
所述热源装置包括热载体承载腔， 所述热载体承载腔与所述熔盐罐 （2) 的夹层之间通过 热载体管道 （20-1 ) 连通；
所述熔盐罐 （2)、 气流粉碎干燥器 （3)、 造粒装置 （5-1 )、 冷却装置 （5-2) 和输出装置 之间通过熔盐管道向连通， 所述熔盐管道由所述熔盐罐 （2) 的下端伸出并连通气流粉碎干燥 器 （3) 的上端； 所述气流粉碎干燥器 （3) 的下端与热交换器 （4) 相连；
所述热源装置指太阳能集热系统（9)、 移动式电伴热（10)或相互独立控制且并联的太阳 能集热系统 （9) 和移动式电伴热 （10);
步骤如下：
将按比例组成的传热蓄热熔盐体系原料加入到所述带夹层的熔盐罐 （2) 中， 启动热源装 置加热到熔融状态后按比例加入石英砂或石墨， 继续加热并搅拌至熔盐体系均匀为止；
将加热均匀的复合熔盐抽至气流粉碎干燥器 （3) 中， 进行气流粉碎和干燥， 得到石英砂 / 石墨复合熔盐传热蓄热介质， 再经过造粒和冷却后由输出装置输出。
所述太阳能集热系统 （9) 与所述熔盐罐之间的热载体管道 （20-1 ) 设为相互独立控制的 两根， 其中一根上设置有高温储存罐 （1 ); 所述高温储存罐 （1 ) 与所述带夹层的熔盐罐 （2) 之间设有热载体泵 （19)。
所述带夹层的熔盐罐（2)与所述气流粉碎干燥器（3)之间的熔盐管道上设置有高温熔盐 泵 （14)。
所述带夹层的熔盐罐（2) 的夹层内腔底部与所述热交换器（4)之间通过一段热载体管道 (20-2) 相连通。
所述热交换器 （4) 与所述热源装置之间通过一段热载体管道 （20-3) 相连通， 所述热载 体管道 （20-3) 上设置有低温储存罐 （18)， 所述低温储存罐 （18) 两端的热载体管道 （20-3 ) 上设置有热载体泵 （16)、 （17)。
所述熔盐罐 （2) 还包括搅拌装置 （11 ) 和进料口 （12)。
所述输出装置依次包括料仓 （6)、 包装装置 （7) 和 /或存储装置 （8)。
任一一段所述热载体管道上至少安装有一个热载体泵。
上述任一方法中采用的熔盐制备设备。
本发明是首次采用石英砂或石墨作为熔盐的复合材料。石英砂是一种坚硬、耐磨化学性能 稳定的硅酸盐矿物， 其主要成分是 Si02， 矿物中常含有少量的杂质成分如 Fe203、 A1203、 CaO、 MgO、 Na20等。 熔点约 1723°C， 沸点约 2230°C， 具有良好的耐高温、 抗氧化、 和 耐化学腐蚀性能。 用于本发明的石英砂采用二氧化硅含量大于 75%的普通石英砂即可。 实验证明， 在硝酸熔盐体系以及碳酸盐熔盐体系中加入石英砂制备所得的传热蓄热介质， 工业成本低， 对蓄热系统腐蚀性甚微， 且与原熔盐体系相比还具有如下的优点和积极效果： 1.本发明制备的传热蓄热介质既有原熔盐体系的传热性能， 又提高了热稳定性和上限使用 温度， 熔盐的凝固点基本不发生变化。 2.本发明制备的熔盐传热蓄热介质的相变潜热大， 储能密度高， 降低了对蓄热系统尺寸和 能量的要求， 能量利用率高， 节能效果好。
本发明的优选实施方案中， 石英砂占 1~50%, 石英砂含量越高， 降低成本越明显； 这个 范围内既能保证熔盐的上限温度提高， 又能保证熔点不升高， 引入的石英砂颗粒度越细越系统 的传热更均匀。
试验数据证明：
本发明在 K2C03-Na2C03二元碳酸盐体系中加入石英砂后， 与原二元碳酸盐相比， 在 800 摄氏度下持续 30小时后损失率明显降低， 说明热稳定性提高； 通过差示扫描仪检测， 显示熔 点降至 540摄氏度左右， 即比原来的工作温度范围更宽， 并且相变潜热增大； 另外一方面， 石 英砂比氯化物成本更低，作为这种损耗性物质的原材料将为太阳能光热发电及工业蓄能领域大 幅度降低成本。
本发明在 K2C03-Na2C03-NaCl-Li2C03体系中加入石英砂后， 与原体系相比， 在 850摄氏 度下维持 30小时后损失率明显下降， 说明热稳定性提高； 通过差示扫描仪检测， 结果显示熔 点降至 350~400摄氏度左右，即比原来的工作温度范围更宽，并且相变潜热增大；另外一方面， 石英砂的加入显著降低了整个体系的原料成本。
本发明采用石英砂对传热蓄热熔盐体系进行改性， 整体上降低了原料成本。但是毫不削弱 原体系的关键特性， 而且使原体系的热稳定性提高， 相变潜热提高， 使用温度范围更宽。 可以 广泛应用于太阳能光热发电产业并有利于促进该产业的发展。
本发明还提供了采用石墨对传热蓄热熔盐体系进行改性的技术方案，由于石墨的特殊结构 而具有的如下特殊性质： 耐高温性、 导电、 导热性、 润滑性、 化学稳定性、 抗热震性， 实验 证明， 本发明提供的加入石墨的传热蓄热介质在热稳定性、 传热性能方面显著提高。
专业术语：
本发明中所称的熔点， 是指采用差示扫描仪在加热过程中常压下检测得出的温度。
本发明还提供了用于规模化制备本发明的碳酸熔盐的制备工艺，其步骤依赖于一套本发明 提出的设备， 该套工艺和设备的创新点及优点如下：
工艺如下：
1.将熔盐体系的不同组分按照一定的顺序依次加入熔盐罐， 在一定的温度和压力条件下， 加热到熔盐罐内的熔盐粘度可机械搅拌时， 开动机械搅拌一段时间至体系均匀。 由热源装置提 供加热所需的能量， 热源装置可选择移动式电伴热或太阳能集热。如果是在用料现场， 比如太 阳能光热电站， 可直接使用聚集的太阳能， 环保节能。
2.开启高温熔盐泵，打开出料口，把熔盐罐内均匀的熔盐体系从气流粉碎干燥器上方注入， 同时热空气自气流粉碎干燥器的底部鼓入干燥器， 二者是逆向的方式。 目的： 使液相的熔盐混 合体系在经过气流粉碎干燥器后直接形成干燥均匀的粉末状，一方面便于包装出售。另外一方 面是使用时性能均一稳定。 自气流干燥器得到的粉末状熔盐经冷却装置降至室温后放入料仓， 包装， 储存。
3.在热源装置是太阳能集热系统的情况下， 可以将熔盐罐夹层中的热载体（高温导热油或 熔盐或过热水蒸气）疏导至热交换器中用于加热所需的热空气， 充分利用了熔盐罐用过之后的 热载体的余热。 整体上提高了该工艺的热能利用率。
优点 1 :
本发明的热源装置提供了以下三种方案：
方案一、本发明采用聚集的太阳能提供的热量作为热源， 节能环保。 可采用四种方式提供 热源： 槽式、 塔式、 碟式、 线性菲涅尔式太阳能光热发电方式的镜场聚集太阳能。 从成本和技 术成熟度的角度优选槽式和塔式。
方式一： 选用光热发电的槽式镜场作为聚集太阳能的方式， 通过集热管中的高温热载体直 接加热熔盐罐。 目前常见的高温热载体是高温熔盐、 导热油、 过热水蒸气， 在槽式镜场中优选 导热油。
方式二： 选用光热发电的塔式镜场作为聚集太阳能的方式， 通过吸热器中的高温热载体直 接加热熔盐罐。 目前常见的高温热载体是高温熔盐、 导热油、 过热水蒸气， 在塔式镜场中优选 熔盐。
方案二、 也可采用移动式电伴热提供热源， 移动式电伴热不同于传统式的缠绕电伴热带， 维修更加的方便简单。
方案三、 太阳能集热系统和移动式电伴热独立控制且并联地使用， 二者可形成互补作用， 比如太阳能辐射不充足时， 可用电伴热进行补充。
优点 2:
进入气流粉碎干燥器的热空气的热量来自于熔盐罐夹层中的热载体的余热，最大效率的利 用热量。
优点 3:
熔盐罐的温度、 压力可控。
优点 4:
最终产品颗粒细小均匀。
附图说明
图 1本发明工艺所用的熔盐制备设备的结构示意图； 其中 1-高温储存罐， 2-熔盐罐， 3-气流粉碎干燥器， 4一热交换器， 5-1 造粒装置、 5-2冷 却装置、 6-料仓， 7-包装装置， 8-存储装置， 9-太阳能集热系统， 10-移动式电伴热， 11-搅拌装 置， 12-进料口， 13-夹层内腔， 14-高温熔盐泵， 15-鼓风机， 16、 17、 18-热载体泵， 18-低温储 存罐， 20-1,20-2， 20-3-热载体管道。
具体实施方式
下面结合具体实施例对本发明进行详细描述。
实验材料：
普通石英砂 （二氧化硅含量大于 75% )， 100目购自山东鸿泰石英砂厂。
石墨： 可商购获得。
硝酸钾， 硝酸钠、 亚硝酸钠、 硝酸铯、 硝酸钙、 硝酸锂： 工业纯， 一般化学用品公司可以 购买到。
碳酸钾、 碳酸钠， 氯化钠， 氯化锂， 工业纯级， 一般化学用品公司可以购买到。
本发明复合有石英砂 /石墨的传热蓄热介质的制备工艺有两种选择：
1、 用于实验室研究的小规模生产可以采用如下步骤：
步骤 1按比例组成熔盐体系， 放入真空加热炉中加热除气除水使其成熔融状态， 加热， 温 度为熔盐相变温度以上 50-100°C。
步骤 2 将石英砂 /石墨按比例加入步骤 (1)熔融的熔盐体系中， 磁力搅拌该熔融混合物 0.5-lh, 保温超声 0.5-2h， 自然冷却， 即制得均匀稳定的石英砂 /石墨复合熔盐。
2、规模化生产优选采用以下工艺及配套的熔盐制备装置： 熔盐制备设备： 熔盐制备设备： 所述设备包括热源装置、带夹层内腔（ 13 )的熔盐罐（ 2 )、气流粉碎干燥器（ 3 )，造粒装置（ 5- 1 )、 冷却装置 （5-2) 和输出装置；
使用中， 将按比例组成的熔盐体系的原料加入到所述带夹层的熔盐罐 （2) 中， 启动热源 装置加热到熔融状态后按比例加入石英砂 /石墨， 继续加热至熔盐体系均匀为止；
将加热均匀的复合熔盐抽至气流粉碎干燥器 （3) 中， 进行气流粉碎和干燥， 得到石英砂 / 石墨复合熔盐传热蓄热介质， 再经过造粒和冷却后由输出装置输出。
所述热源装置包括热载体承载腔， 所述热载体承载腔与所述夹层内腔（13)之间通过热载 体管道 (20-1 ) 连通；
所述熔盐罐 （2)、 气流粉碎干燥器 （3)、 造粒装置 （5-1 )、 冷却装置 （5-2) 和输出装置 之间通过熔盐管道向连通， 所述熔盐管道由所述熔盐罐 （2) 的下端伸出并连通气流粉碎干燥 器 （3) 的上端； 所述气流粉碎干燥器 （3) 的下端与热交换器 （4) 相连； 熔盐罐内均匀的熔 盐体系从上方抽入气流粉碎干燥器中， 同时热空气自气流粉碎干燥器的底部鼓入干燥器， 二者 是逆向的方式。 目的： 使液相的熔盐混合体系在经过气流粉碎干燥器后直接形成干燥均匀的粉 末状， 一方面便于包装出售。 另外一方面是使用时性能均一稳定；
所述热源装置指太阳能集热系统（9)、 移动式电伴热（10)或相互独立控制且并联的太阳 能集热系统（9)和移动式电伴热（10); 该设备中热源装置可以是单独的所述太阳能集热系统 9 或单独的移动式电伴热， 也可以是相互独立控制且并联的太阳能集热系统 （9) 和移动式电 伴热 （10)。
所述太阳能集热系统 （9) 与所述熔盐罐之间的热载体管道 （20-1 ) 设为相互独立控制的 两根， 其中一根上设置有高温储存罐 （1 ) 所述太阳能集热系统 9与所述高温储存罐 1之间设 有阀门， 用于控制太阳能集热系统 9中的热载体向高温储存罐 1中流动； 当关闭该阀门时， 可 以使用太阳能集热系统 9或是移动式电伴热 10直接加热热载体进而加热熔盐罐 2的方式来制 备高温熔盐； 当能源充足或熔盐罐不需要加热时， 可打开太阳能集热系统与高温储存罐 1之间 的阀门， 经过太阳能集热系统加热的热载体便可通过管道流向高温储存罐进而储存起来， 当需 要加热时， 可以通过热载体泵 (19)抽进夹层内腔 （13) 进而加热熔盐罐 （2) 来制备高温熔盐。
优选所述熔盐罐 (2)与所述气流粉碎干燥器 (3)之间的熔盐管道上设置有高温熔盐泵（14)。 用于将加热后的熔盐抽至气流粉碎干燥器中。
优选所述带夹层的熔盐罐 （2) 的夹层内腔（13)底部与所述热交换器（4)之间通过一段 热载体管道 （20-2) 相连通。 该段热载体管道 （20-2) 用于将夹层内腔 （13) 中的热载体引导 至热交换器 （4) 中用于加热该设备中所需的热空气。 从而实现夹层内腔 （13) 内的热载体的 余热再利用， 节能环保。
优选所述热交换器 （4) 与所述热源装置之间通过一段热载体管道 （20-3 ) 相连通， 所述 热载体管道（20-3)上设置有低温储存罐（18)，所述低温储存罐（18)两端的热载体管道（20-3) 上设置有热载体泵 （16)、 （17)。 在热交换器中被用尽热量的热载体冷却后通过所述热载体管 道 （20-3) 上的热载体泵 （16) 抽送至低温储存罐中， 通过热载体泵 （17) 送回到热源装置中 循环使用。
优选所述熔盐罐 （2) 还包括搅拌装置 （11 ) 和进料口 （12)。
优选所述输出装置依次包括造料仓 （6)、 包装装置 （7) 和 /或存储装置 （8)。
每一段所述热载体管道至少设置有一个热载体泵。
上述设备中的各段管道上均设置有充足的阀门用于控制管道中的物质的流动和流向。热源 装置与带夹层的熔盐罐之间的热载体管道上的阀门通过控制热载体的输输送量和速度从而控 制加热温度， 所述熔盐罐自身带有压力控制装置。
实施例 1~3.二元硝酸盐体系 KN03-NaN03中加入石英砂制备蓄热传热介质 步骤 1.按表 1所列的配方准备组成二元硝酸熔盐体系的材料，放入反应釜中， 加热搅拌使固体 完全熔融， 然后保温 0.5-lh， 加热温度为熔盐相变温度以上 80-120°C。
步骤 2.搅拌条件下， 将石英砂分散到熔融的二元硝酸熔盐体系中， 继续搅拌 l-2h， 混合物呈胶 状，
表 1.各实施例中的二元硝酸熔盐体系配方
Figure imgf000011_0001
加入的石英砂 （规格为 100目） 按以下比例梯度进行:
第 1组： 石英砂在三种石英砂复合二元硝酸熔盐传热蓄热介质中占 1%， 得第 1~3个产品。 第 2组： 石英砂在三种石英砂复合二元硝酸熔盐传热蓄热介质中占 10%， 得第 4~6个产品。 第 3组： 石英砂在三种石英砂复合二元硝酸熔盐传热蓄热介质中占 20%， 得第 7~9个产品。 第 4组： 石英砂在三种石英砂复合二元硝酸熔盐传热蓄热介质中占 30%， 得第 10~12个产 f 第 5组： 石英砂在三种石英砂复合二元硝酸熔盐传热蓄热介质中占 40%， 得第 13~15个产 f 第 6组： 石英砂在三种石英砂复合二元硝酸熔盐传热蓄热介质中占 50%， 得第 16~18个产 每一个产品的对照为该产品对应的二元硝酸熔盐。
步骤 3.相变潜热测试和熔点测试：
采用通用的差示扫描仪 DSC进行 （常压下扫描）。
测试结果显示， 与对照相比， 相变潜热都明显增大；
石英砂复合二元硝酸熔盐编号 KN03-NaN03熔盐体系重量百分比配比 （同时也是对照） 表 2.熔点的测试结果
石英砂复合二元硝酸熔盐编号 熔点。 c
对照:硝酸钾 10% ; 硝酸钠 90% 270
1 250
4 254
7 256
10 270
13 274 16 278
对照:硝酸钾 40 硝酸钠 60 % 220
2 205
5 207
8 203
11 219
14 228
17 231
对照:硝酸钾 60 硝酸钠 40 % 210
3 198
6 199
9 193
12 210
15 213
18 212 而第 1~3组产品熔点有所下降但不显著； 第 5组和第 6组产品的熔点稍微有所提高。 步骤 4.热稳定性测试
对制备得到 18种传热蓄热介质及 3种对照二元硝酸熔盐进行热稳定性测试。
测试采用重量法进行： 将实施例 1~3所得的 18种熔融盐分别装入镍制的坩埚中， 放入温 控炉中进行加热， 从常温开始进行实验， 每隔一段时间取出实验坩埚用分析天平称重。 如果在 某一温度段内， 试样的重量不再减少， 再提高温控炉的温度。然后再每隔一段时间取出实验坩 埚进行称重， 到另一个稳态之后再继续升温。
四种对照二元硝酸体系的稳定温度界限均为 550°C， 550°C下加热 100小时， 损失率可达 10%； 加热 30小时， 损失率达 5%。， 710热 100小时， 损失率可达 25% ，加热 30小时， 损失 率达 13%。
对实施例 1~3所得的 3组 18种传热蓄热介质进行热稳定性测试，
表 3.55CTC下的损失率统计结果
时间 （小时） 30 100
产品组号
第一组 <5 <10 第二组 <3.8 <7
第三组 <3.5 <6. 5%
第四组 <3.2 <6.1
第五组 <2.9 <5.5
第六组 <3 <5
加入石英砂能够使各组产品的热稳
表 4.71CTC下的损失率统计结果
时间 （小时） 30 100
产品组号
第一组 <10.2 <22
第二组 <7.6 <16.2
第三组 <6.5 <14.5
第四组 <5.5 <13.0
第五组 <5.1 <12
第六组 <5.1 <11 可以看出在 71CTC度下， 加入非常少的石英砂， 能够使各组产品的热稳定性相对于对照明 显提高。
实施例 4~7.二元硝酸盐体系 KN03-NaN02中加入石英砂制备蓄热传热介质
步骤 1.按表 5所列的配方准备组成二元硝酸熔盐体系的材料，放入反应釜中， 加热搅拌使固体 完全熔融， 然后保温 0.5-lh， 加热温度为熔盐相变温度以上 80-120°C。
步骤 2.搅拌条件下， 将石英砂分散到熔融的二元硝酸熔盐体系中， 继续搅拌 l-2h， 混合物呈胶 状，
表 5.各实施例中的二元硝酸熔盐体系配方
Figure imgf000013_0001
加入的石英砂 （规格为 100目） 按以下比例梯度进行: 第 1组： 石英砂在四种石英砂复合二元硝酸熔盐传热蓄热介质中占 1%， 得第 1~4个产品。 第 2组： 石英砂在四种石英砂复合二元硝酸熔盐传热蓄热介质中占 10%， 得第 5~8个产品。 第 3组： 石英砂在四种石英砂复合二元硝酸熔盐传热蓄热介质中占 20%， 得第 9~12个产品 < 第 4组： 石英砂在四种石英砂复合二元硝酸熔盐传热蓄热介质中占 30%， 得第 13~16个产 n n 第 5组： 石英砂在四种石英砂复合二元硝酸熔盐传热蓄热介质中占 40%， 得第 17~20个产 第 6组： 石英砂在四种石英砂复合二元硝酸熔盐传热蓄热介质中占 50%， 得第 21~24个产 n n 每一个产品的对照为该产品对应的二元硝酸熔盐。
步骤 3.相变潜热测试和熔点测试：
采用通用的差示扫描仪 DSC进行 （常压下扫描）。
测试结果显示， 与对照相比， 相变潜热都明显增大；
表 6.熔点的测试结果
石英砂复合二元硝酸熔盐编号 熔点。 c
对照： 硝酸钾： 30份； 亚硝酸钠： 70份 207
1 197
5 195
9 193
13 199
17 213
21 220
对照： 硝酸钾： 40份； 亚硝酸钠： 60份 133
2 125
6 118
10 115
14 123
18 140
22 142
对照： 硝酸钾： 45份； 亚硝酸钠： 55份 132
3 122
7 121
11 119
15 126 19 138
23 141
对照： 硝酸钾： 55份； 亚硝酸钠： 45份 133
4 126
8 120
12 117
16 125
20 139
24 145
而第：1~4组产品熔点有所下降； 第 5组和第 6组产品的熔点稍微有所提高。
步骤 4.热稳定性测试
对制备得到 24种传热蓄热介质及 4种对照二元硝酸熔盐进行热稳定性测试。
测试采用重量法进行： 将实施例 5~8所得的 24种熔融盐分别装入镍制的坩埚中， 放入温 控炉中进行加热， 从常温开始进行实验， 每隔一段时间取出实验坩埚用分析天平称重。 如果在 某一温度段内， 试样的重量不再减少， 再提高温控炉的温度。然后再每隔一段时间取出实验坩 埚进行称重， 到另一个稳态之后再继续升温。
四种对照二元硝酸体系的稳定温度界限均为 500°C， 500°C下加热 100小时， 损失率可达 12%； 加热 30小时， 损失率达 5%。， 600°C下加热 100小时， 损失率可达 22%; 加热 30小时， 损失率达 12%。
对实施例 4~7所得的 6组 24种传热蓄热介质进行热稳定性测试，
表 7.50CTC下的损失率统计结果
Figure imgf000015_0001
可以看出在 50CTC度下， 加入石英砂能够使各组产品的热稳定性相对于对照明显提高。
表 8.60CTC下的损失率统计结果 时间 （小时） 30 100
产品组号
第一组 <9 <20
第二组 <7.6 <17
第三组 <6.5 <12
第四组 <5.8 <10
第五组 <5.6 <8.4
第六组 <5.3 % <7.9
可以看出在 60CTC度下， 加入非常少的石英砂， 能够使各组产品的热稳定性相对于对照明 显提高。
实施例 8~11.三元硝酸盐体系 KN03-NaN03-NaN02中加入石英砂制备蓄热传热介质
步骤 1.按表 9所列的配方准备组成三元硝酸熔盐体系的材料，放入反应釜中， 加热搅拌使固体 完全熔融， 然后保温 0.5-lh， 加热温度为熔盐相变温度以上 50-100°C。
表 9.三元硝酸熔盐体系的材料
Figure imgf000016_0001
步骤 2.搅拌条件下， 将石英砂分散到熔融的三元硝酸熔盐体系中， 继续搅拌 l-2h， 混合物呈胶 状，
加入的石英砂 （规格为 100目） 按以下比例梯度进行：
第一组：石英砂在四种石英砂复合三元硝酸熔盐传热蓄热介质中占 1%，得第 1~4个产品。 第二组： 石英砂在四种石英砂复合三元硝酸熔盐传热蓄热介质中占 10%， 得第 5~8个产
Π
ΡΠ。
第三组： 石英砂在四种石英砂复合三元硝酸熔盐传热蓄热介质中占 25%， 得第 9~12个产 第四组： 石英砂在四种石英砂复合三元硝酸熔盐传热蓄热介质中占 40%， 得第 13~16个 口
广口口。
第五组： 石英砂在四种石英砂复合三元硝酸熔盐传热蓄热介质中占 50%， 得第 17~20个 口
广口口。
步骤 3.相变潜热测试和熔点测试。
采用通用的差示扫描仪 DSC进行 （常压下扫描）。
测试结果显示， 与对照相比， 相变潜热都明显增大； 第 1~3 组产品熔点基本不变， 第 4 组和第 5组产品的熔点稍微有所提高。
步骤 4.热稳定性测试
对制备得到 20种传热蓄热介质及对照三元硝酸熔盐进行热稳定性测试。
测试采用重量法进行： 将实施例 8-11所得的 20种熔融盐分别装入镍制的坩埚中， 放入温 控炉中进行加热， 从常温开始进行实验， 每隔一段时间取出实验坩埚用分析天平称重。 如果在 某一温度段内， 试样的重量不再减少， 再提高温控炉的温度。然后再每隔一段时间取出实验坩 埚进行称重， 到另一个稳态之后再继续升温。
对照三元硝酸体系的稳定温度界限为 500°C， 500°C下加热 100小时， 损失率可达 25%， 加热 30小时， 损失率达 10%。 600°C下加热 100小时， 损失率可达 30%， 加热 30小时， 损失 率达 15%。 700°C °C下加热 100小时， 损失率可达 35%， 加热 30小时， 损失率达 24%。
对实施例 8~11所得的 5组 20种传热蓄热介质进行热稳定性测试，
表 10.60CTC下的损失率统计结果
时间 （小时） 30 100
产品组号
第一组 8-10% 22-26%
第二组 7-9% 18-20%
第三组 4-6% 15-20%
第四组 2-3% 12-16%
第五组 2-4% 12-16% 表 11.70CTC下的损失率统计结果
时间 （小时） 30 100
产品组号 第一组 15-20% 25-30%
第二组 12-15% 20-23%
第三组 10-13% 18-20%
第四组 8-12% 15-18%
第五组 9-12% 15-18%
可以看出在 600°C和 700°C度下， 加入石英砂， 能够使各组产品的热稳定性相对于对照明 显提高。
实施例 12~14 .三元硝酸盐体系 KN03-NaN03-Ca (N03) 中加入石英砂制备蓄热传热介质 步骤 1.2按表 12所列的配方制备石英砂复合三元硝酸熔盐， 方法同实施例 8~11步骤 1、 2 的方法。
表 12.三元硝酸熔盐的材料
Figure imgf000018_0001
加入的石英砂按梯度进行：
第一组：石英砂在三种石英砂复合三元硝酸熔盐传热蓄热介质中占 1%，得第 1~3个产品。 第二组： 石英砂在四种石英砂复合三元硝酸熔盐传热蓄热介质中占 30%， 得第 4~6个产
Π
ΡΠ。
第三组： 石英砂在四种石英砂复合三元硝酸熔盐传热蓄热介质中占 50%， 得第 7~9个产
Π
ΡΠ。
步骤 3.相变潜热测试和熔点测试。
采用通用的差示扫描仪 DSC进行 （常压下扫描）。
测试结果显示， 相变潜热都明显增大； 与对照相比， 第一组和第二组熔点基本不变， 第三 组熔点有所提高。
步骤 4.热稳定性测试 对制备得到 9种传热蓄热介质及对照三元硝酸熔盐进行热稳定性测试。
测试采用重量法进行：将实施例 12~14所得的 9种熔融盐分别装入镍制的坩埚中，放入温 控炉中进行加热， 从常温开始进行实验， 每隔一段时间取出实验坩埚用分析天平称重。 如果在 某一温度段内， 试样的重量不再减少， 再提高温控炉的温度。然后再每隔一段时间取出实验坩 埚进行称重， 到另一个稳态之后再继续升温。
对照三元硝酸体系的稳定温度界限为 550°C， 550°C下加热 30小时， 损失率约 3%， 加热 50小时时损失率为约 6%; 650°C下加热 30小时， 损失率约 5%， 加热 50小时时损失率为约 10%； 750°C下加热 30小时， 损失率约 7%， 加热 50小时时损失率为约 15%;
下加热 30小时， 损失率约 7%,热 50小时时损失率为约 12
对实施例 12~14所得的 3组 9种传热蓄热介质进行热稳定性测试，
表 13.65CTC下的损失率统计结果
Figure imgf000019_0001
表 14.75CTC下的损失率统计结果
Figure imgf000019_0002
可以看出， 本发明的产品在 75CTC的损失率与对照在 55CTC的损失率相当， 说明， 本发明 的产品具有更好的热稳定性， 能够在 75CTC下稳定操作较长时间。
实施例 15~17.多元硝酸盐体系 KN03-NaN03-NaN02-CsN03中加入石英砂制备蓄热传热介质 步骤 1.石英砂复合多元硝酸熔盐产品 1~3的制备：
按表 15所列 15~17配方准备组成多元硝酸熔盐体系的材料，加热搅拌均匀后加入石英砂， 继续加热搅拌， 以除气除水， 加热温度为熔盐相变温度以上 80-120°C。
将石英砂 （100目）分散到熔融的多元硝酸熔盐体系中， 搅拌该熔融混合物 l-2h， 得石英 砂复合多元硝酸熔盐传热蓄热介质。 石英砂在产品 1~3中分别占 1%， 20%, 50%。 表 15.各实施例中的多元硝酸体系配方
实施例 多元硝酸盐体系 多元硝酸盐体系配方
编号
15 KN03-NaN03-NaN02-CsN03体系 硝酸钾 80份， 硝酸钠 5份， 亚硝酸 钠 20份， 硝酸铯 1
16 硝酸钾 40份， 硝酸钠 15份， 亚硝 酸钠 50份， 硝酸铯 10份
17 硝酸钾 60份， 硝酸钠 10份， 亚硝 酸钠 30份， 硝酸铯 5份
18 KN03-NaN03-NaN02-Ca(N03)2体 硝酸钾 40份， 硝酸钠 15份， 亚硝 酸钠 50份， 硝酸钙 10份
19 硝酸钾 80份， 硝酸钠 5份； 亚硝酸 钠 20份， 硝酸钙 1份
20 硝酸钾 60份， 硝酸钠 10份， 亚硝 酸钠 30份， 硝酸钙 5份
21 KN03-NaN03-NaN02-LiN03体系 硝酸钾 80份， 硝酸钠 5份， 亚硝酸 钠 20份， 硝酸锂 1份；
22 硝酸钾 40份， 硝酸钠 15份， 亚硝 酸钠 50份； 硝酸锂 10份；
23 硝酸钾 60份， 硝酸钠 10份， 亚硝 酸钠 40份； 硝酸锂 8份；
24 KN03-NaN03-CsN03-Ca(N03)2体 硝酸钾 80份， 硝酸钠 5份， 硝酸铯
20份， 硝酸钙 5份；
25 硝酸钾 60份， 硝酸钠 10份， 硝酸 铯 40份， 硝酸钙 10份；
26 硝酸钾 40份， 硝酸钠 15份， 硝酸 铯 50份， 硝酸钙 1份；
27 KN03-NaN03- LiN03-CsN03体系 硝酸钾 60份， 硝酸钠 8份， 硝酸锂
20份， 硝酸铯 10份；
28 硝酸钾 80份， 硝酸钠 5份， 硝酸锂
30份， 硝酸铯 10份； 29 硝酸钾 40份， 硝酸钠 15份， 硝酸 锂 50份， 硝酸铯 6份；
30 KN03-NaN03-NaN02- 硝酸钾 70份， 硝酸钠 5份， 亚硝酸
CsN03-Ca(N03)2体系 钠 30份， 硝酸铯 10份， 硝酸钙 20
份
31 硝酸钾 40份， 硝酸钠 15份， 亚硝
酸钠 50份， 硝酸铯 20份， 硝酸钙
30份。
32 硝酸钾 80份， 硝酸钠 10份， 亚硝
酸钠 10份， 硝酸铯 30份， 硝酸钙
10份
步骤 2.石英砂复合多元硝酸熔盐产品 1~3的热稳定性测试
对制备得到的传热蓄热介质及对照多元硝酸熔盐进行热稳定性测试。
测试采用重量法进行：将实施例 15~17所得的 3种熔融盐分别装入镍制的坩埚中，放入温 控炉中进行加热， 从常温开始进行实验， 每隔一段时间取出实验坩埚用分析天平称重。 如果在 某一温度段内， 试样的重量不再减少， 再提高温控炉的温度。然后再每隔一段时间取出实验坩 埚进行称重， 再到另一个稳态之后再继续升温。
结果显示：
石英砂复合多元硝酸熔盐产品 1~3的熔盐 600°C下保温 120小时， 损失率均少于 1%;
700 °C下保温 30小时， 三个产品的损失率分别约为 20%， 3%, 1%。
对照为未加石英砂的三种多元硝酸体系熔盐 （表 15实施例 15-17编号 1~3对应的体系） ， 在 600 °C下可运行 30小时损失率约为 8%， 但是在 700 °C下出现明显的损失， 运行至 30小时， 损失率达 25%。
说明加入石英砂能有效改善了硝酸熔盐体系在高温下的稳定性及提高使用上限温度。 步骤 3.石英砂复合多元硝酸熔盐产品 1~3的相变潜热测试和熔点测试。
采用通用的差示扫描仪 DSC进行 （在常压下进行扫描）。
测试结果显示， 与对照相比， 相变潜热都明显增大； 产品 1、 2的熔点基本不变， 产品 3 的熔点稍微有所提高。
实施例 18~20.多元硝酸盐体系 KN03-NaN03-NaN02-Ca(N03)2中加入石英砂制备蓄热传热介 质
按表 15所列的配方准备组成多元硝酸熔盐体系的材料。 产品 4~6的制备方法及检测方法完全同实施例 15~17，石英砂（100目）分别占 10%， 25%, 40%； 对照不含石英砂， 为表 15中实施例 15~17对应的体系。
热稳定性测定结果与实施例 15~17相似， 在 700 °C下保温 30小时后， 本发明制备得到的 三种产品的损失率依次约 10%、 3 1%, 明显低于对照的最高 28%。
采用通用的差示扫描仪 DSC进行（在常压下进行扫描）。 测试结果显示， 与对照相比， 相 变潜热都明显增大； 熔点基本不变。
实施例 21~23.多元硝酸盐体系 KN03-NaN03-NaN02-LiN03中加入石英砂制备蓄热传热介质 按表 15所列的配方准备组成多元硝酸熔盐体系的材料
制备方法及检测方法完全同实施例 15~17。
产品 7~9所加的石英砂 （100目） 占 15%， 30%, 45%
热稳定性测定结果与实施例 15~17相似， 在 700°C下保温 30小时后， 本发明制备得到的 三种产品的损失率最高 12%， 4%、 2%, 明显低于对照的 30%。
采用通用的差示扫描仪 DSC进行（在常压下进行扫描）。 测试结果显示， 与对照相比， 产 品 7~9的熔点基本不变， 相变潜热有所增大。
实施例 24~26.多元硝酸盐体系 KN03-NaN03-CsN03-Ca(N03)2中加入石英砂制备蓄热传热介 质
产品 10~12的制备方法及检测方法完全同实施例 15~17，
石英砂 (100目）分别占 10%， 25%, 45%； 对照不含石英砂， 为表 15中实施例 25~27对应 的体系。
热稳定性测定结果与实施例 15~17非常相似， 在 700°C下保温 30小时后， 本发明制备得 到的三种产品的损失率最高 12%， 3%, 2%, 明显低于对照的 30%。
采用通用的差示扫描仪 DSC进行 （在常压下进行扫描）。 测试结果显示， 与对照相比， 相 变潜热有所增大， 产品 10~11的熔点基本无变化， 产品 12的熔点略微有所提高。
实施例 27~32.其它多元硝酸盐体系中加入石英砂制备蓄热传热介质
产品 13~18的制备方法及检测方法完全同实施例 16~18，每种多元硝酸熔盐体系的三种配 方所配比的石英砂 （100目） 比例分别为： 15%， 25%, 40%； 对照不含石英砂， 为表 15中实 施例 27~32对应的体系。
热稳定性测定结果， 在 70CTC下保温 30小时后， 本发明制备得到的 6种产品的损失率最 高 11%， 2.5% 1%, 明显低于对照的 30%。
采用通用的差示扫描仪 DSC进行（在常压下进行扫描）。 测试结果显示， 与对照相比， 产 品 13~18的熔点基本不变， 相变潜热有所增大。 上述实验结果说明： 本发明在多元硝酸熔盐体系中加入石英砂制备所得的传热蓄热介质， 对蓄热系统腐蚀性甚微， 且与原多元硝酸熔盐体系相比带来了以下几方面的进步：
既有硝酸熔盐的传热性能， 又提高了多元硝酸熔盐的上限使用温度； 使用温度范围更宽， 热稳定性好。
相变潜热大， 储能密度高， 降低了对蓄热系统尺寸和能量的要求， 能量利用率高， 节能效 果好。
本发明制备的熔盐传热蓄热介质导热性能大大增加， 克服了硝酸熔盐导热性能差， 易局部 过热的缺点， 可广泛用于太阳能光热发电技术领域。
实施例 33~36.石英砂-二元碳酸熔盐复合体系
二元碳酸盐体系配方如表 16。
表 16.各实施例中的二元碳酸熔盐体系配方
Figure imgf000023_0001
步骤 1.按表 16所列的配方准备组成二元碳酸熔盐体系的材料， 放入反应釜中， 加热搅拌使固 体完全熔融， 然后保温 0.5-lh， 加热温度为熔盐相变温度以上 80-120°C。
步骤 2.搅拌条件下， 按以下实验设计的比例将石英砂分散到熔融的二元碳酸熔盐体系中， 继续 搅拌 l-2h， 得石英砂复合碳酸熔盐， 呈胶状。
本发明实验设计所加石英砂 （规格为 100目） 按以下比例梯度进行：
第 1组： 石英砂在四种石英砂复合二元碳酸熔盐传热蓄热介质中占 1%， 得第 1~4个产品。 第 2组： 石英砂在四种石英砂复合二元碳酸熔盐传热蓄热介质中占 10%， 得第 5~8个产品。 第 3组： 石英砂在四种石英砂复合二元碳酸熔盐传热蓄热介质中占 20%， 得第 9~12个产品。 第 4组： 石英砂在四种石英砂复合二元碳酸熔盐传热蓄热介质中占 30%， 得第 13~16个产品。 第 5组： 石英砂在四种石英砂复合二元碳酸熔盐传热蓄热介质中占 40%， 得第 17~20个产品。 第 6组： 石英砂在四种石英砂复合二元碳酸熔盐传热蓄热介质中占 50%， 得第 21~24个产品。
每一个产品的对照为该产品对应的原二元碳酸熔盐体系。
步骤 3.相变潜热测试和熔点测试：
采用通用的差示扫描仪 DSC进行 （常压下扫描）。 测试结果显示， 与对照相比， 相变潜热都明显增大；
相比对照而言， 第 1~4组产品熔点都有所降低， 熔点在 530~560摄氏度之间； 第 5组和第 6组产品的熔点稍微有所提高， 在 600摄氏度左右。
步骤 4.热稳定性测试
对制备得到 24种传热蓄热介质及 4种对照二元碳酸熔盐进行热稳定性测试。
测试采用重量法进行： 将实施例 33-36所得的 24种熔融盐分别装入镍制的坩埚中， 放入 温控炉中进行加热， 从常温开始进行实验， 每隔一段时间取出实验坩埚用分析天平称重。 如果 在某一温度段内， 试样的重量不再减少， 再提高温控炉的温度。然后再每隔一段时间取出实验 坩埚进行称重， 到另一个稳态之后再继续升温。
结果显示： 四种对照二元碳酸体系的热稳定性表现如下：
800°C加热 100小时， 损失率达 8%；
850°C加热 30小时， 损失率达 8%;
900°C加热 30小时， 损失率达 12%。
对实施例 33-36所得的 6组 24种传热蓄热介质进行热稳定性测试结果见表 17:
表 17.各温度条件下的损失率统计结果
Figure imgf000024_0001
可以看出， 加入石英砂能够使各组产品的热稳定性相对于对照明显提高。
实施例 37~40.石英砂-含锂碳酸熔盐复合体系
含锂碳酸熔盐体系如表 18。
表 18.各实施例中的含锂碳酸熔盐体系配方
实施例 含锂碳酸熔盐体系 含锂碳酸熔盐体系配方 （重量份） - -对照 编号
37 K2C03-Na2C03-NaCl-Li2C03 碳酸钾： 20份； 碳酸钠： 40份； 氯化钠： 20份； 碳酸锂： 10份
38 碳酸钾： 25份； 碳酸钠： 35份； 氯化钠：
10份； 碳酸锂： 8份
49 碳酸钾： 45份； 碳酸钠： 25份； 氯化钠：
20份； 碳酸锂： 5份
40 碳酸钾： 60份； 碳酸钠： 20份； 氯化钠：
10份； 碳酸锂： 10份
步骤 1.按表 18所列的配方准备组成含锂碳酸熔盐体系的材料， 放入反应釜中加热搅拌使固体 完全熔融， 然后保温 0.5-lh， 加热温度为熔盐相变温度以上 80-120°C。
步骤 2.搅拌条件下， 按以下实验设计的比例将石英砂分散到熔融的含锂碳酸熔盐体系中， 继续 搅拌 l-2h， 得石英砂复合碳酸熔盐， 呈胶状，
本发明实验设计所加石英砂 （规格为 100目） 按以下比例梯度进行：
第 1组： 石英砂在四种石英砂复合碳酸熔盐传热蓄热介质中占 1%， 得第 25~28个产品。
第 2组： 石英砂在四种石英砂复合碳酸熔盐传热蓄热介质中占 10%， 得第 29~32个产品。 第 3组： 石英砂在四种石英砂复合碳酸熔盐传热蓄热介质中占 20%， 得第 33~36个产品。 第 4组： 石英砂在四种石英砂复合碳酸熔盐传热蓄热介质中占 30%， 得第 37~40个产品。 第 5组： 石英砂在四种石英砂复合二元碳酸熔盐传热蓄热介质中占 40%， 得第 41~44个产品。 第 6组： 石英砂在四种石英砂复合二元碳酸熔盐传热蓄热介质中占 50%， 得第 45~48个产品。
每一个产品的对照为该产品对应的原含锂碳酸熔盐体系。
步骤 3.相变潜热测试和熔点测试：
采用通用的差示扫描仪 DSC进行 （常压下扫描）。
测试结果显示， 与对照相比， 相变潜热都明显增大；
相比对照而言，
第 1~4组产品熔点都有所降低， 熔点在 320~380摄氏度之间；
第 5组和第 6组产品的熔点稍微有所提高， 在 400~410摄氏度左右。
步骤 4.热稳定性测试
对制备得到 24种传热蓄热介质及 4种对照含锂碳酸熔盐进行热稳定性测试。
测试采用重量法进行： 将实施例 37~40所得的 24种熔融盐分别装入镍制的坩埚中， 放入 温控炉中进行加热， 从常温开始进行实验， 每隔一段时间取出实验坩埚用分析天平称重。 如果 在某一温度段内， 试样的重量不再减少， 再提高温控炉的温度。然后再每隔一段时间取出实验 坩埚进行称重， 到另一个稳态之后再继续升温。 结果显示： 四种对照含锂碳酸体系的热稳定性表现如下：
850°C加热 100小时， 损失率约 5%;
900°C加热 30小时， 损失率约 6%;
950°C加热 30小时， 损失率约 10%。
对实施例 37~40所得的 6组 24种传热蓄热介质进行热稳定性测试结果见表 19:
表 19.各温度条件下的损失率统计结果
Figure imgf000026_0001
可以看出加入石英砂能够使各组产品的热稳定性相对于对照明显提高。
实施例 41~43.三元硝酸盐体系 KN03-NaN03-Ca (N03) 中加入石墨制备蓄热传热介质
采用实施例 12~14的三元硝酸熔盐体系， 方法同实施例 8~11步骤 1的方法。
加入的石墨按梯度进行：
实施例 41 为第一组： 石墨在三种石英砂复合三元硝酸熔盐传热蓄热介质中占 1%， 得第
1-3个产品。
实施例 42为第二组： 石墨在四种石英砂复合三元硝酸熔盐传热蓄热介质中占 30%， 得第 4-6个产品。
实施例 43为第三组： 石墨在四种石英砂复合三元硝酸熔盐传热蓄热介质中占 50%， 得第 7-9个产品
步骤 3.相变潜热测试和熔点测试。
采用通用的差示扫描仪 DSC进行 （常压下扫描）。
测试结果显示， 相变潜热都明显增大； 与对照相比， 第一组和第二组熔点基本不变， 第三 组熔点有所提高。
步骤 4.热稳定性测试
对制备得到 9种传热蓄热介质及对照三元硝酸熔盐进行热稳定性测试。
测试采用重量法进行： 将 9种熔融盐分别装入镍制的坩埚中， 放入温控炉中进行加热， 从 常温开始进行实验， 每隔一段时间取出实验坩埚用分析天平称重。如果在某一温度段内， 试样 的重量不再减少， 再提高温控炉的温度。然后再每隔一段时间取出实验坩埚进行称重， 到另一 个稳态之后再继续升温。
对照三元硝酸体系的稳定温度界限为 550°C， 550°C下加热 30小时， 损失率约 3%， 加热 50小时时损失率为约 8% ; 650°C下加热 30小时， 损失率约 5.5%， 加热 50小时时损失率为约 12%； 750°C下加热 30小时， 损失率约 9%， 加热 50小时时损失率为约 17%。
对实施例 41-43所得 9种传热蓄热介质进行热稳定性测试，
表 19.65CTC下的损失率统计结果
Figure imgf000027_0001
表 20.75CTC下的损失率统计结果
Figure imgf000027_0002
可以看出， 本发明的产品在 75CTC的损失率与对照在 55CTC的损失率相当， 结果与加入石 英砂相近， 能够在 750°C下稳定操作较长时间。

Claims

权利要求书
1.复合有石英砂的传热蓄热介质， 其特征在于： 是通过在传热蓄热熔盐体系中加入石英砂 复合而成。
2.根据权利要求 1所述的传热蓄热介质， 其特征在于： 所述传热蓄热熔盐体系为硝酸熔盐 体系、 碳酸熔盐体系。
3.根据权利要求 2所述的传热蓄热介质， 所述传热蓄热熔盐体系为二元硝酸熔盐体系， 所 述二元硝酸熔盐体系占传热蓄热介质总重量的 50~99%， 所述石英砂占传热蓄热介质总重量的 1~50%。
4.根据权利要求 3所述的传热蓄热介质， 所述二元硝酸熔盐体系占传热蓄热介质总重量的 50-80%, 所述石英砂占传热蓄热介质总重量的 20~50%。
5.根据权利要求 4所述的传热蓄热介质， 所述二元硝酸熔盐体系占传热蓄热介质总重量的 60-80%, 所述石英砂占传热蓄热介质总重量的 20~40%。
6.根据权利要求 5所述的传热蓄热介质， 所述二元硝酸熔盐体系占传热蓄热介质总重量的 60-70%, 所述石英砂占传热蓄热介质总重量的 30~40%
7.根据权利要求 3~6任一所述的传热蓄热介质， 所述二元硝酸熔盐体系为 KN03-NaN03 体系： 其中硝酸钾： 30-60份； 硝酸钠： 30-60份。
8.根据权利要求 3~6任一所述的石英砂复合二元硝酸熔盐传热蓄热介质，所述二元硝酸熔 盐体系为 KN03-NaN02体系： 其中硝酸钾： 30-60份； 亚硝酸钠： 40-70份。
9.根据权利要求 2所述的传热蓄热介质， 所述传热蓄热熔盐体系为三元硝酸熔盐体系， 所 述三元硝酸熔盐体系占传热蓄热介质总重量的 50~99%， 所述石英砂占传热蓄热介质总重量的 1~50%。
10.根据权利要求 9 所述的传热蓄热介质， 所述硝酸熔盐体系占传热蓄热介质总重量的 50-90%, 所述石英砂占传热蓄热介质总重量的 10~50%。
11.根据权利要求 9或 10所述的传热蓄热介质，所述三元硝酸熔盐体系及其重量组分如下: KN03-NaN03-NaN02体系: 其中硝酸钾： 40-80份; 硝酸钠： 5-15份; 亚硝酸钠： 10-50份。
12.根据权利要求 9或 10所述的传热蓄热介质，所述三元硝酸熔盐体系及其重量组分如下: KN03-NaN03-Ca(N03)2体系: 其中硝酸钾： 5-40份; 硝酸钠： 5-25份; 硝酸钙： 10-70份。
13.根据权利要求 2所述的传热蓄热介质， 所述传热蓄热熔盐体系为多元硝酸熔盐体系， 所述多元硝酸熔盐体系占传热蓄热介质总重量的 50~99%， 所述石英砂占传热蓄热介质总重量 的 1~50%。
14.根据权利要求 13所述的传热蓄热介质， 所述多元硝酸熔盐体系占传热蓄热介质总重量 的 50~90%， 石英砂占 10~50%。
15.根据权利要求 13 或 14 所述的传热蓄热介质， 所述多元硝酸熔盐体系为 KN03-NaN03-NaN02-CsN03 体 系 、 KN03-NaN03-NaN02-Ca(N03)2 体 系 、 KN03-NaN03-NaN02-LiN03 体系、 KN03-NaN03-CsN03-Ca(N03)2 体系、 KN03-NaN03- LiN03-CsN03体系或 KN03-NaN03-NaN02-CsN03-Ca(N03)2体系。
16.根据权利要求 15所述的传热蓄热介质，
所述 KN03-NaN03-NaN02-CsN03体系的重量组分如下： 硝酸钾 40份 -80份， 硝酸钠 5份 -15份， 亚硝酸钠 20-50份， 硝酸铯 1份 -10份；
所述 KN03-NaN03-NaN02-Ca(N03)2体系的组分如下：硝酸钾 40份 -80份，硝酸钠 5份 -15 份，； 亚硝酸钠 20份 -50份， 硝酸钙 1份 -10份；
所述 KN03-NaN03-NaN02-LiN03体系的组分如下： 硝酸钾 40份 -80份， 硝酸钠 5份 -15 份， 亚硝酸钠 20份 -50份; 硝酸锂 1份 -10份；
所述 KN03-NaN03-CsN03-Ca(N03)2体系的组分如下： 硝酸钾 40份 -80份，硝酸钠 5份 -15 份， 硝酸铯 20份 -50份， 硝酸钙 1份 -10份；
所述 KN03-NaN03- LiN03-CsN03体系的组分如下： 硝酸钾 40份 -80份， 硝酸钠 5份 -15 份， 硝酸锂 20份 -50份， 硝酸铯 1份 -10份；
所述 KN03-NaN03-NaN02-CsN03-Ca(N03)2的组分如下： 硝酸钾 40份 -80份， 硝酸钠 5份 -15份， 亚硝酸钠 10份 -50份， 硝酸铯 10份 -30份， 硝酸钙 10份 -30份。
17.根据权利要求 2 所述的传热蓄热介质， 所述传热蓄热熔盐体系为碳酸熔盐体系： K2C03-Na2C03。
18.根据权利要求 17所述的传热蓄热介质， 所述 K2C03-Na2CO体系中的重量组分为碳酸 钾 30~60份， 碳酸钠 30~60份。
19.根据权利要求 2 所述的传热蓄热介质， 所述传热蓄热熔盐体系为碳酸熔盐体系： K2C03-Na2C03-NaCl-Li2C03体系， 所述 K2C03-Na2C03-NaCl-Li2C03体系中的重量组分为： 碳酸钾： 20-60份、 碳酸钠： 20-40份、 碳酸锂： 10-20份、 氯化钠： 5-10份。
20.根据权利要求 17~19任一所述的传热蓄热介质， 所述石英砂在所述传热蓄热介质中所 占的比例为 1~50%；
所述石英砂在所述传热蓄热介质中所占的比例为 10~40%；
所述石英砂在所述传热蓄热介质中所占的比例为 20~45%；
或所述石英砂在所述传热蓄热介质中所占的比例为 30~40%。
21.—种复合有石墨的传热蓄热介质， 其特征在于： 在传热蓄热熔盐体系中复合石墨而得。
22.根据权利要求 21 所述的传热蓄热介质， 所述传热蓄热熔盐体系指 KN03-NaN03-Ca(N03)2： 其中硝酸钾： 5-40份； 硝酸钠： 5-25份； 硝酸钙： 10-70份， 石墨占 1-50%.
23.权利要求 1~22任一所述的传热蓄热介质在工业蓄能或太阳能光热发电中的用途。
24.用于制备权利要求 1~22任一所述传热蓄热介质的制备工艺，其特征在于采用以下熔盐 制备设备：
所述设备包括热源装置、 带夹层的熔盐罐 （2)、 气流粉碎干燥器 （3)、 造粒装置 （5-1 )、 冷却装置 （5-2) 和输出装置；
所述热源装置包括热载体承载腔， 所述热载体承载腔与所述熔盐罐 （2) 的夹层之间通过 热载体管道 （20-1 ) 连通；
所述熔盐罐 （2)、 气流粉碎干燥器 （3)、 造粒装置 （5-1 )、 冷却装置 （5-2) 和输出装置 之间通过熔盐管道向连通， 所述熔盐管道由所述熔盐罐 （2) 的下端伸出并连通气流粉碎干燥 器 （3) 的上端； 所述气流粉碎干燥器 （3) 的下端与热交换器 （4) 相连；
所述热源装置指太阳能集热系统（9)、 移动式电伴热（10)或相互独立控制且并联的太阳 能集热系统 （9) 和移动式电伴热 （10);
步骤如下：
将按比例组成的传热蓄热熔盐体系原料加入到所述带夹层的熔盐罐 （2) 中， 启动热源装 置加热到熔融状态后按比例加入石英砂或石墨， 继续加热并搅拌至熔盐体系均匀为止；
将加热均匀的复合熔盐抽至气流粉碎干燥器 （3) 中， 进行气流粉碎和干燥， 得到石英砂 / 石墨复合熔盐传热蓄热介质， 再经过造粒和冷却后由输出装置输出。
25.根据权利要求 24所述的方法， 其特征在于： 所述太阳能集热系统 （9) 与所述熔盐罐 之间的热载体管道 （20-1 )设为相互独立控制的两根， 其中一根上设置有高温储存罐 （1 ); 所 述高温储存罐 （1 ) 与所述带夹层的熔盐罐 （2) 之间设有热载体泵 （19)。
26.根据权利要求 24所述的方法， 其特征在于： 所述带夹层的熔盐罐 （2) 与所述气流粉 碎干燥器 （3) 之间的熔盐管道上设置有高温熔盐泵 （14)。
27.根据权利要求 24所述的方法， 其特征在于： 所述带夹层的熔盐罐 （2) 的夹层内腔底 部与所述热交换器 （4) 之间通过一段热载体管道 （20-2) 相连通。
28.根据权利要求 27所述的方法， 其特征在于： 所述热交换器 （4) 与所述热源装置之间 通过一段热载体管道 （20-3) 相连通， 所述热载体管道 （20-3) 上设置有低温储存罐 （18)， 所述低温储存罐 （18) 两端的热载体管道 （20-3) 上设置有热载体泵 （16)、 （17)。
29.根据权利要求 24所述的方法， 其特征在于： 所述熔盐罐 （2) 还包括搅拌装置 （11 ) 和 进料口 （12)。
30.根据权利要求 24~29所述的方法， 其特征在于： 所述输出装置依次包括料仓 （6)、 包装 装置 （7) 和 /或存储装置 （8)。
31.根据权利要求 24~29所述的方法， 其特征在于： 任一一段所述热载体管道上至少安装有 一个热载体泵。
32.权利要求 24-31任一方法中采用的熔盐制备设备。
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